Method for dyeing keratinous material, comprising the use of an organosilicon compound, a colored effect pigment and a sealing reagent i

ABSTRACT

The subject of the present disclosure is a process for dyeing keratinous material, in particular human hair, comprising the following steps:
         Application of an agent (a) to the keratinous material, wherein the agent (a) comprises:   (a1) at least one organic silicon compound selected from the group of silanes having one, two or three silicon atoms, and   (a2) at least one coloring compound comprising at least one effect pigment which comprises α) a substrate platelet and β) a coating, wherein the coating has at least one layer which is       (i) a metal oxide and/or metal oxide hydrate and   (ii) a coloring compound from the group of pigments,
 
and
       application of an agent (b) to the keratinous material, wherein the agent (b) comprises:   (b1) at least one sealing reagent.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371based on International Application No. PCT/EP2020/068979, filed Jul. 6,2020, which was published under PCT Article 21(2) and which claimspriority to German Application No. 102019210686.2, filed Jul. 19, 2019,which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The subject of the present application is a method for treatingkeratinous material, in particular human hair, which comprises theapplication of two agents (a) and (b). The agent (a) is exemplified byits content of at least one organic silicon compound (a1) and at leastone selected coloring compound (a2). The agent (b) comprises at leastone sealing reagent.

A further subject of this application is a multi-component packagingunit (kit-of-parts) for dyeing keratinous material, in particular humanhair, which comprises separately prepared at least three agent (a′),(a″) and (b). Agents (a′) and (a″) can be used to prepare the agent (a)used in the process described above.

BACKGROUND

The change in shape and color of keratin fibers, especially hair, is akey area of modern cosmetics. To change the hair color, the expert knowsvarious coloring systems depending on coloring requirements. Oxidationdyes are usually used for permanent, intensive dyeing's with goodfastness properties and good grey coverage. Such dyes usually containoxidation dye precursors, so-called developer components and couplercomponents, which form the actual dyes with one another under theinfluence of oxidizing agents, such as hydrogen peroxide. Oxidation dyesare exemplified by very long-lasting dyeing results.

When direct dyes are used, ready-made dyes diffuse from the colorantinto the hair fiber. Compared to oxidative hair dyeing, the dyeing'sobtained with direct dyes have a shorter shelf life and quicker washability. Dyeing with direct dyes usually remain on the hair for a periodof between 5 and 20 washes.

The use of color pigments is known for short-term color changes on thehair and/or skin. Color pigments are understood to be insoluble,coloring substances. These are present undissolved in the dyeformulation in the form of small particles and are only deposited fromthe outside on the hair fibers and/or the skin surface. Therefore, theycan usually be removed without residue by a few washes withsurfactant-comprising cleaning agents. Various products of this type areavailable on the market under the name hair mascara.

If the user wants particularly long-lasting dyeing's, the use ofoxidative dyes has so far been his only option. However, despitenumerous optimization attempts, an unpleasant ammonia or amine odorcannot be completely avoided in oxidative hair dyeing. The hair damagestill associated with the use of oxidative dyes also has a negativeeffect on the user's hair.

EP 2168633 B1 deals with the task of producing long-lasting haircolorations using pigments. The paper teaches that when the combinationof a pigment, an organic silicon compound, a film-forming polymer and asolvent is used on hair, it is possible to produce colorations that areparticularly resistant to shampooing.

Metallic luster pigments or metallic effect pigments are widely used inmany fields of technology. They are used, for example, to colorcoatings, printing inks, inks, plastics, glasses, ceramic products andpreparations for decorative cosmetics such as nail polish. They areexemplified by their attractive angle-dependent color impression(goniochromism) and their metallic-looking luster.

Hair with a metallic finish or metallic highlights are in trend. Themetallic tone makes the hair look thicker and shinier.

There is a need to provide hair dyes with effect pigments that on theone hand have high wash and rub fastness and on the other hand do notnegatively affect hair properties such as manageability and feel. Forthis purpose, it would be desirable if the effect pigments used had ahigh covering power and could be applied to the hair in thin layers. Itwould be desirable if the hair could be colored intensively and in manydifferent shades with the help of the effect pigments.

BRIEF SUMMARY

Processes and kits-of-parts for dyeing keratinous material are providedherein. In an embodiment, a process for dyeing keratinous material isprovided, comprising:

-   -   applying an agent (a) to the keratinous material, wherein the        agent (a) comprises:    -   (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and    -   (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is

(i) a metal oxide and/or metal oxide hydrate and

(ii) a coloring compound chosen from the group of pigments; and

-   -   applying an agent (b) to the keratinous material, wherein the        agent (b) comprises: (b1) at least one sealing reagent.

In another embodiment, a kit-of-parts for dyeing keratinous material isprovided. The kit-of-parts includes, separately packaged

-   -   a first container containing an agent (a′), wherein the agent        comprises (a′): (a1) at least one organic silicon compound        selected from the group of silanes having one, two or three        silicon atoms, and    -   a second container containing an agent (a″), the agent (a″)        comprising: (a2) at least one colorant compound comprising at        least one effect pigment comprising α) a substrate platelet and        β) a coating, wherein the coating has at least one layer that is

(i) a metal oxide and/or metal oxide hydrate and

(ii) a coloring compound chosen from the group of pigments,

a third container containing an agent (b), wherein the agent (b)comprises: (b1) at least one sealing reagent.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and isnot intended to limit the disclosure or the application and uses of thesubject matter as described herein. Furthermore, there is no intentionto be bound by any theory presented in the preceding background or thefollowing detailed description.

The task of the present disclosure was to provide a coloring system witheffect pigments that has fastness properties comparable to oxidativecoloring. Wash fastness properties should be outstanding, but the use ofoxidation dye precursors normally used for this purpose should beavoided. For this purpose, the coloring system should be available formany different shades.

Surprisingly, it has now been found that the task can be excellentlysolved if keratinous materials, in particular human hair, are colored bya process in which at least two agents (a) and (b) are applied to thekeratinous materials (hair). Here, the first agent (a) comprises atleast one organic silicon compound from the group of silanes with one,two or three silicon atoms, and further at least one selected coloringcompound. In the agent (a), the organic silicon compound and thecolorant compound are thus prepared together. The second agent (b)comprises at least one sealing reagent.

When the two agents (a) and (b) were used in a dyeing process,keratinous material could be dyed with particularly high color intensityand high fastness properties.

A first object of the present disclosure is a method for coloringkeratinous material, in particular human hair, comprising the followingsteps:

-   -   Application of an agent (a) to the keratinous material, wherein        the agent (a) comprises:        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments,        and    -   Application of an agent (b) to the keratinous material, wherein        the agent (b) comprises:        (b1) at least one sealing reagent.

In the work leading to the present disclosure, it has been found thatthe preferential successive application of agents (a) and (b) enablesthe production of very stable and washfast colorations on the keratinousmaterials. Without being limited to this theory, it is suspected in thiscontext that the joint application of organic silicon compound (a1) andcolor-imparting compound (a2) leads to the formation of a particularlyresistant first film on the keratinous material. The first layer issealed with the application of the second agent (b). For example, afilm-forming polymer is now deposited on this first layer as a sealingreagent (b1) in the form of a further film.

Due to this special type of packaging—i.e., the joint application ofsilane (a1) and color-imparting compound (a2) and separate applicationof the sealing reagent (b1)—the film system produced in this wayexhibited improved resistance to external influences. In this way, thecolorant compounds (a2) were permanently fixed to the keratinousmaterial, so that extremely washfast colorations with good resistance toshampooing could be obtained.

In addition, depending on the structure of the effect pigment, dependingon the colorant compound (ii) from the group of pigments used, differentcolor shades could be obtained on the dyed keratinous hair. For example,colorings with a metallic sheen or colorings with a brightening effectcould be obtained.

Keratinous Material

Keratinous material includes hair, skin, nails (such as fingernailsand/or toenails). Wool, furs and feathers also fall under the definitionof keratinous material.

Preferably, keratinous material is understood to be human hair, humanskin and human nails, especially fingernails and toenails. Keratinousmaterial is understood to be human hair.

Agent (a) and (b)

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous material, in particular human hair. The two agent (a)and (b) are different from each other.

In other words, a first object of the present disclosure is a method fortreating keratinous material, in particular human hair, comprising thefollowing steps:

Application of an agent (a) to the keratinous material, wherein theagent (a) comprises:(a1) at least one organic silicon compound selected from the group ofsilanes having one, two or three silicon atoms, and(a2) at least one colorant compound comprising at least one effectpigment comprising α) a substrate platelet and β) a coating, wherein thecoating has at least one layer that is(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigmentsandApplication of an agent (b) to the keratinous material, wherein theagent (b) comprises: (b1) at least one sealing reagent.

Agent (a)

Preferably, the agent (a) comprises the ingredients (a1) and (a2)essential to the present disclosure in a cosmetic carrier, particularlypreferably in an aqueous or aqueous-alcoholic cosmetic carrier. Thiscosmetic carrier can be liquid, gel or cream. Pasty, solid or powderycosmetic carriers can also be used for the preparation of agent (a). Forhair treatment, in particular hair coloring, such carriers are, forexample, creams, emulsions, gels or also surfactant-comprising foamingsolutions, such as shampoos, foam aerosols, foam formulations or otherpreparations suitable for application to the hair.

Preferably, the cosmetic carrier comprises—based on its weight—at least2% by weight of water. Further preferably, the water content is above10% by weight, still further preferably above 20% by weight andparticularly preferably above 40% by weight. The cosmetic carrier canalso be aqueous-alcoholic. Aqueous/alcoholic solutions in the context ofthe present disclosure are aqueous solutions comprising 2 to 70% byweight of a C₁-C₄ alcohol, more particularly ethanol or isopropanol. Theagents as contemplated herein may additionally contain other organicsolvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or1,2-propylene glycol. Preferred are all water-soluble organic solvents.

Organic Silicon Compounds from the Group of Silanes (a1)

As an ingredient (a1) essential to the present disclosure, the agent (a)comprises at least one organic silicon compound from the group ofsilanes having one, two or three silicon atoms.

Particularly preferably, the agent (a) comprises at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, the organic silicon compound comprising one or morehydroxyl groups and/or hydrolysable groups per molecule.

These organic silicon compounds (a1) or organic silanes included in theagent (a) is reactive compounds.

Organic silicon compounds, alternatively called organosilicon compounds,are compounds which either have a direct silicon-carbon bond (Si—C) orin which the carbon is bonded to the silicon atom via an oxygen,nitrogen or sulfur atom. The organic silicon compounds of the presentdisclosure are compounds comprising one to three silicon atoms. Organicsilicon compounds preferably contain one or two silicon atoms.

According to IUPAC rules, the term silane chemical compounds based on asilicon skeleton and hydrogen. In organic silanes, the hydrogen atomsare completely or partially replaced by organic groups such as(substituted) alkyl groups and/or alkoxy groups. In organic silanes,some of the hydrogen atoms may also be replaced by hydroxy groups.

In a particularly preferred embodiment, an agent (a) is applied to thekeratinous material, said agent (a) comprising at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, said organic silicon compound further comprising one ormore hydroxyl groups or hydrolysable groups per molecule.

In a very particularly preferred embodiment, an agent (a) to thekeratinous material, said agent (a) comprising at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, said organic silicon compound further comprising one ormore basic chemical functions and one or more hydroxyl groups orhydrolysable groups per molecule.

This basic group or basic chemical function can be, for example, anamino group, an alkylamino group or a dialkylamino group, which ispreferably connected to a silicon atom via a linker. Preferably, thebasic group is an amino group, a C₁-C₆ alkylamino group or adi(C₁-C₆)alkylamino group.

The hydrolysable group(s) is (are) preferably a C₁-C₆ alkoxy group,especially an ethoxy group or a methoxy group. It is preferred when thehydrolysable group is directly bonded to the silicon atom. For example,if the hydrolysable group is an ethoxy group, the organic siliconcompound preferably comprises a structural unit R′R″R′″Si—O—CH2-CH3. Theresidues R′, R″ and R′″ represent the three remaining free valences ofthe silicon atom.

In a very particularly preferred embodiment the agent (a) comprises atleast one organic silicon compound selected from silanes having one, twoor three silicon atoms, the organic silicon compound preferablycomprising one or more basic chemical functions and one or more hydroxylgroups or hydrolysable groups per molecule.

Particularly satisfactory results were obtained when the agent (a)comprises at least one organic silicon (a1) compound of formula (I)and/or (II).

The compounds of formulas (I) and (II) are organic silicon compoundsselected from silanes having one, two or three silicon atoms, theorganic silicon compound comprising one or more hydroxyl groups and/orhydrolysable groups per molecule.

In another very particularly preferred embodiment, an agent is appliedto the keratinous material (or human hair), the agent (a) comprising atleast one organic silicon compound (a) of formula (I) and/or (II),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

-   -   where    -   R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl        group,    -   L is a linear or branched bivalent C₁-C₂₀ alkylene group,

R₃ is a hydrogen atom or a C₁-C₆ alkyl group,

R₄ represents a C₁-C₆ alkyl group

-   -   a, represents an integer from 1 to 3, and    -   b stands for the integer 3−a,

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R₅, R₅′, R₅″ independently represent a hydrogen atom or a C₁-C₆        alkyl group,    -   R₆, R₆′ and R₆″ independently represent a C₁-C₆ alkyl group,    -   A, A′, A″, A′″ and A″″ independently represent a linear or        divalent, bivalent C₁-C₂₀ alkylene group,    -   R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl        group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an        amino C₁-C₆ alkyl group or a group of formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III),

-   -   c, stands for an integer from 1 to 3,    -   d stands for the integer 3−c,    -   c′ stands for an integer from 1 to 3,    -   d′ stands for the integer 3−c′,    -   c″ stands for an integer from 1 to 3,    -   d″ stands for the integer 3−c″,    -   e stands for 0 or 1,    -   f stands for 0 or 1,    -   g stands for 0 or 1,    -   h stands for 0 or 1,    -   provided that at least one of e, f, g and h is different from 0.

The substituents R₁, R₂, R₃, R₄, R₅, R₅′, R₅″, R₆, R₆′, R₆″, R₇, R₈, L,A, A′, A″, A′″ and A″″ in the compounds of formula (I) and (II) areexplained below as examples: Examples of a C₁-C₆ alkyl group are thegroups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl,n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkylradicals. Examples of a C₂-C₆ alkenyl group are vinyl, allyl,but-2-enyl, but-3-enyl and isobutenyl, preferred C₂-C₆ alkenyl radicalsare vinyl and allyl. Preferred examples of a hydroxy C₁-C₆ alkyl groupare a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred.Examples of an amino C₁-C₆ alkyl group are the aminomethyl group, the2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group isparticularly preferred. Examples of a linear bivalent C₁-C₂₀ alkylenegroup include the methylene group (—CH2-), the ethylene group(—CH2-CH2-), the propylene group (—CH2-CH2-CH2-), and the butylene group(—CH2-CH2-CH2-CH2-). The propylene group (—CH2-CH2-CH2-) is particularlypreferred. From a chain length of 3 C atoms, bivalent alkylene groupscan also be branched. Examples of branched divalent, bivalent C₃-C₂₀alkylene groups are (—CH₂—CH(CH₃)—) and (—CH₂—CH(CH₃)—CH₂—).

In the organic silicon compounds of the formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

the radicals R₁ and R₂ independently of one another represent a hydrogenatom or a C₁-C₆ alkyl group. Very preferably, R₁ and R₂ both represent ahydrogen atom.

In the middle part of the organic silicon compound is the structuralunit or the linker -L- which stands for a linear or branched, divalentC₁-C₂₀ alkylene group.

A divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachL grouping may form two bonds. One bond is from the amino group R₁R₂N tothe linker L, and the second bond is between the linker L and thesilicon atom.

Preferably, -L- represents a linear, divalent (i.e., divalent) C₁-C₂₀alkylene group. Further preferably -L- stands for a linear bivalentC₁-C₆ alkylene group. Particularly preferred -L stands for a methylenegroup (—CH₂—), an ethylene group (—CH₂—CH₂—), propylene group(—CH₂—CH₂—CH₂—) or butylene (—CH₂—CH₂—CH₂—CH₂—). L stands for apropylene group (—CH₂—CH₂—CH₂—)

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

The organic silicon compounds of formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

one end of each carries the silicon-comprising group—Si(OR₃)_(a)(R₄)_(b).

In the terminal structural unit —Si(OR₃)_(a)(R₄)_(b), R₃ is hydrogen orC₁-C₆ alkyl group, and R₄ is C₁-C₆ alkyl group. R₃ and R₄ independentlyof each other represent a methyl group or an ethyl group.

Here a stands for an integer from 1 to 3, and b stands for the integer3−a. If a stands for the number 3, then b is equal to 0. If a stands forthe number 2, then b is equal to 1. If a stands for the number 1, then bis equal to 2.

Particularly resistant films could be produced if the agent (a)comprises at least one organic silicon compound (a1) of formula (I) inwhich the radicals R₃, R₄ independently of one another represent amethyl group or an ethyl group.

When using the process for dyeing keratinous material, dyeing's with thebest wash fastnesses could be obtained analogously when the agent (a)comprises at least one organic silicon compound of formula (I) in whichthe radicals R₃, R₄ independently of one another represent a methylgroup or an ethyl group.

Furthermore, dyeing's with the best wash fastnesses could be obtained ifthe agent (a) comprises at least one organic silicon compound of theformula (I) in which the radical a represents the number 3. In this casethe radical b stands for the number 0.

In a further preferred embodiment, the agent (a) used in the processcomprises at least one organic silicon compound (a1) of formula (I),wherein

-   -   R₃, R₄ independently of one another represent a methyl group or        an ethyl group and    -   a stands for the number 3 and    -   b stands for the number 0.

In another preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) of formula (I),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

-   -   R₁, R₂ both represent a hydrogen atom, and    -   L represents a linear, bivalent C₁-C₆-alkylene group, preferably        a propylene group (—CH₂—CH₂—CH₂—) or an ethylene group        (—CH₂—CH₂—),    -   R₃ represents a hydrogen atom, an ethyl group or a methyl group,    -   R₄ represents a methyl group or an ethyl group,    -   a stands for the number 3 and    -   b stands for the number 0.

Organic silicon compounds of the formula (I) which are particularlysuitable for solving the problem as contemplated herein are

In a further preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) selected from the group of

-   (3-Aminopropyl)triethoxysilane-   (3-Aminopropyl)trimethoxysilane-   1-(3-Aminopropyl)silantriol-   (2-Aminoethyl)triethoxysilane-   (2-Aminoethyl)trimethoxysilane-   1-(2-Aminoethyl)silantriol-   (3-Dimethylaminopropyl)triethoxysilane-   (3-Dimethylaminopropyl)trimethoxysilane-   1-(3-Dimethylaminopropyl)silantriol-   (2-Dimethylaminoethyl)triethoxysilane.-   (2-Dimethylaminoethyl)trimethoxysilane and/or-   1-(2-dimethylaminoethyl)silanetriol.

The organic silicon compounds of formula (I) are commercially available.(3-aminopropyl)trimethoxysilane, for example, can be purchased fromSigma-Aldrich. Also (3-aminopropyl)triethoxysilane is commerciallyavailable from Sigma-Aldrich.

In a further embodiment, the composition comprises at least one organicsilicon compound (a1) of formula (II)

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

The organosilicon compounds of formula (II) each bear at their two endsthe silicon-comprising groupings (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c′),

In the central part of the molecule of formula (II) there are the groups-(A)_(e)- and —[NR₇-(A′)]_(f)- and —[O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-.Here, each of the radicals e, f, g and h can independently of oneanother stand for the number 0 or 1, with the proviso that at least oneof the radicals e, f, g and h is different from 0. In other words, anorganic silicon compound of formula (II) comprises at least one groupingselected from the group of -(A)- and —[NR₇-(A′)]- and —[O-(A″)]- and—[NR₈-(A′″)]-.

In the two terminal structural units (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c′), the radicals R5, R5′, R5″ independently of oneanother represent a hydrogen atom or a C₁-C₆ alkyl group. The radicalsR6, R6′ and R6″ independently represent a C₁-C₆ alkyl group.

Here c stands for an integer from 1 to 3, and d stands for the integer3−c. If c stands for the number 3, then d is equal to 0. If c stands forthe number 2, then d is equal to 1. If c stands for the number 1, then dis equal to 2.

Analogously c′ stands for a whole number from 1 to 3, and d′ stands forthe whole number 3−c′. If c′ stands for the number 3, then d′ is 0. Ifc′ stands for the number 2, then d′ is 1. If c′ stands for the number 1,then d′ is 2.

Films with the highest stability or dyes with the best wash fastnessescould be obtained when the residues c and c′ both stand for the number3. In this case d and d′ both stand for the number 0.

In another preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R₅ and R₅′ independently represent a methyl group or an ethyl        group,    -   c and c′ both stand for the number 3 and    -   d and d′ both stand for the number 0.

If c and c′ are both the number 3 and d and d′ are both the number 0,the organic silicon compound of the present disclosure corresponds toformula (IIa)

(R₅O)₃Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(OR₅′)₃  (IIa).

The radicals e, f, g and h can independently stand for the number 0 or1, whereby at least one radical from e, f, g and h is different fromzero. The abbreviations e, f, g and h thus define which of the groupings-(A)_(e)- and —[NR₇-(A′)]_(f)- and —[O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-are in the middle part of the organic silicon compound of formula (II).

In this context, the presence of certain groupings has proved to beparticularly beneficial in terms of increasing washability. Particularlysatisfactory results were obtained when at least two of the residues e,f, g and h stand for the number 1. Especially preferred e and f bothstand for the number 1. Furthermore, g and h both stand for the number0.

If e and f both stand for the number 1 and g and h both stand for thenumber 0, the organic silicon compound as contemplated hereincorresponds to formula (IIb)

(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]-Si(R₆′)_(d′)(OR₅′)_(c′)  (IIb).

The radicals A, A′, A″, A′″ and A″″ independently represent a linear ordivalent, bivalent C₁-C₂₀ alkylene group. Preferably the radicals A, A′,A″, A′″ and A″″ independently of one another represent a linear,bivalent C₁-C₂₀ alkylene group. Further preferably the radicals A, A′,A″, A′″ and A″″ independently represent a linear bivalent C₁-C₆ alkylenegroup. In particular, the radicals A, A′, A″, A′″ and A″″ independentlyof one another represent a methylene group (—CH₂—), an ethylene group(—CH₂—CH₂—), a propylene group (—CH₂—CH₂—CH₂—) or a butylene group(—CH₂—CH₂—CH₂—CH₂—). Very preferably, the radicals A, A′, A″, A′″ andA″″ represent a propylene group (—CH₂—CH₂—CH₂—).

The divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachgrouping A, A′, A″, A′″ and A″″ may form two bonds.

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

If the radical f represents the number 1, then the organic siliconcompound of formula (II) comprises a structural grouping —[NR₇-(A′)]-.

If the radical h represents the number 1, then the organic siliconcompound of formula (II) comprises a structural grouping —[NR₈-(A′″)]-.

Wherein R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkylgroup, a hydroxy-C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, anamino-C₁-C₆ alkyl group or a group of the formula (III)

(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III).

Very preferably the radicals R₇ and R₈ independently of one anotherrepresent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a2-alkenyl group, a 2-aminoethyl group or a grouping of the formula(III).

If the radical f represents the number 1 and the radical h representsthe number 0, the organic silicon compound comprises the grouping[NR₇-(A′)] but not the grouping —[NR₈-(A′″)]. If the radical R₇ nowstands for a grouping of the formula (III), the agent (a) comprises anorganic silicon compound with 3 reactive silane groups.

In another preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   e and f both stand for the number 1,    -   g and h both stand for the number 0,    -   A and A′ independently represent a linear, divalent C₁-C₆        alkylene group        and    -   R₇ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl        group, a 2-alkenyl group, a 2-aminoethyl group or a group of        formula (III).

In a further preferred embodiment, the agent (a) comprises at least oneorganic silicon compound of formula (II), wherein

-   -   e and f both stand for the number 1,    -   g and h both stand for the number 0,    -   A and A′ independently of one another represent a methylene        group (—CH₂—), an ethylene group (—CH₂—CH₂—) or a propylene        group (—CH₂—CH₂—CH₂), and    -   R₇ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl        group, a 2-alkenyl group, a 2-aminoethyl group or a group of        formula (III).

Organic silicon compounds of formula (II) which are well suited forsolving the problem as contemplated herein are:

The organic silicon compounds of formula (II) are commerciallyavailable.

Bis(trimethoxysilylpropyl)amines with the CAS number 82985-35-1 can bepurchased from Sigma-Aldrich.Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2 canbe purchased from Sigma-Aldrich, for example.N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamineis alternatively referred to asBis(3-trimethoxysilylpropyl)-N-methylamine and can be purchasedcommercially from Sigma-Aldrich or Fluorochem.3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine withthe CAS number 18784-74-2 can be purchased for example from Fluorochemor Sigma-Aldrich.

In a further preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) selected from the group of

-   3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine-   3-(Triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamine-   N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine-   N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)    propyl]-1-propanamine-   2-[Bis[3-(trimethoxysilyl) propyl]amino]-ethanol-   2-[Bis[3-(triethoxysilyl) propyl]amino]ethanol-   3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)    propyl]-1-propanamine-   3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl) propyl]-1-propanamine-   N1,N1-Bis[3-(trimethoxysilyl) propyl]-1,2-ethanediamine,-   N1,N1-Bis[3-(triethoxysilyl) propyl]-1,2-ethanediamine,-   N,N-Bis[3-(trimethoxysilyl)propyl]-2-Propen-1-amine and/or-   N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.

In further tests, in particular dyeing tests, it has also been found tobe particularly advantageous if the agent (a) applied to the keratinousmaterial in the process comprises at least one organic silicon compoundof the formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

The compounds of formula (IV) are organic silicon compounds selectedfrom silanes having one, two or three silicon atoms, the organic siliconcompound comprising one or more hydroxyl groups and/or hydrolysablegroups per molecule.

The organic silicon compound(s) of formula (IV) may also be called asilane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

where

-   -   R₉ stands for a C₁-C₁₈ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

where

-   -   R₉ stands for a C₁-C₁₈ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, the agent (a) comprises, in additionto the organic silicon compound or compounds of formula (I), at leastone further organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

where

-   -   R₉ stands for a C₁-C₁₈ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, the agent (a) comprises, in additionto the organic silicon compound or compounds of formula (II), at leastone further organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

where

-   -   R₉ stands for a C₁-C₁₈ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In a further preferred embodiment, the agent (a) comprises, in additionto the organic silicon compound or compounds of formula (I) and/or (II),at least one further organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

where

-   -   R₉ stands for a C₁-C₁₈ alkyl group,    -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,    -   R₁₁ represents a C₁-C₆ alkyl group    -   k is an integer from 1 to 3, and    -   m stands for the integer 3−k.

In the organic silicon compounds of formula (IV), the radical R₉represents a C₁-C₁₈ alkyl group. This C₁-C₁₈ alkyl group is saturatedand can be linear or branched. Preferably, R₉ represents a linear C₁-C₁₈alkyl group. Preferably, R₉ represents a methyl group, an ethyl group,an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexylgroup, an n-octyl group, an n-dodecyl group or an n-octadecyl group.Particularly preferably, R₉ represents a methyl group, an ethyl group,an n-propyl group, an n-hexyl group or an n-octyl group.

In the organic silicon compounds of form (IV), the R₁₀ radicalrepresents a hydrogen atom or a C₁-C₆ alkyl group. Especiallypreferably, R₁₀ stands for a methyl group or an ethyl group.

In the organic silicon compounds of form (IV), the radical R₁ representsa C₁-C₆ alkyl group. Particularly preferably, R₁ represents a methylgroup or an ethyl group.

Furthermore, k stands for a whole number from 1 to 3, and m stands forthe whole number 3−k. If k stands for the number 3, then m is equal to0. If k stands for the number 2, then m is equal to 1. If k stands forthe number 1, then m is equal to 2.

Particularly stable films, i.e., dyeing's with particularly good washfastness properties, could be obtained if an agent (a) comprising atleast one organic silicon compound (a1) corresponding to formula (IV):in which the radical k is the number 3, was used in the process. In thiscase the radical m stands for the number 0.

Organic silicon compounds of the formula (IV) which are particularlysuitable for solving the problem as contemplated herein are

In another preferred embodiment, the agent (a) comprises at least oneorganic silicon compound (a1) of formula (IV) selected from the group of

-   -   Methyltrimethoxysilane    -   Methyltriethoxysilane    -   Ethyltrimethoxysilane    -   Ethyltriethoxysilane    -   Propyltrimethoxysilane    -   Propyltriethoxysilane    -   Hexyltrimethoxysilane    -   Hexyltriethoxysilane    -   Octyltrimethoxysilane    -   Octyltriethoxysilane    -   Dodecyltrimethoxysilane    -   Dodecyltriethoxysilane.    -   Octadecyltrimethoxysilane and/or    -   Octadecyltriethoxysilane.

The organic silicon compounds described above are reactive compounds. Inthis context, it has been found preferable if the agent (a)comprises—based on the total weight of the agent (a)—one or more organicsilicon compounds (a1) in a total amount of 0.1 to 20% by weight,preferably 1 to 15% by weight and particularly preferably 2 to 8% byweight.

In a further preferred embodiment, the agent (a) comprises—based on thetotal weight of the agent (a)—one or more organic silicon compounds (a1)in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weightand particularly preferably 2 to 8% by weight.

To achieve particularly good dyeing results, it is particularlyadvantageous to use the organic silicon compounds of the formula (I)and/or (II) in certain quantity ranges on average (a). Particularlypreferably, the agent (a) comprises—based on the total weight of theagent (a)—one or more organic silicon compounds of the formula (I)and/or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to5% by weight and particularly preferably 0.5 to 3% by weight.

In a further preferred embodiment, the agent (a) comprises—based on thetotal weight of the agent (a)—one or more organic silicon compounds ofthe formula (I) and/or (II) in a total amount of 0.1 to 10% by weight,preferably 0.5 to 5% by weight and particularly preferably 0.5 to 3% byweight.

Furthermore, it has proven to be particularly preferred if the organicsilicon compound(s) of formula (IV) is (are) also present in certainquantity ranges in average (a). Particularly preferably, the agent (a)comprises—based on the total weight of the agent (a) —one or moreorganic silicon compounds of the formula (IV) in a total amount of 0.1to 20% by weight, preferably 2 to 15% by weight and particularlypreferably 4 to 9% by weight.

In a further preferred embodiment, the agent (a) comprises—based on thetotal weight of the agent (a)—one or more organic silicon compounds ofthe formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2to 15% by weight and particularly preferably 3.2 to 10% by weight.

In the course of the work leading to this present disclosure, it wasfound that particularly stable and uniform films could be obtained onthe keratinous material even when the agent (a) included two organicsilicon compounds that were structurally different from each other.

In another preferred embodiment, the agent (a) comprises at least twostructurally different organic silicon compounds.

In a preferred embodiment, an agent (a) comprising at least one organicsilicon compound of formula (I) and at least one organic siliconcompound of formula (IV) is applied to the keratinous material.

In an explicitly very particularly preferred embodiment, there isapplied to the keratinous material an agent (a) comprising at least oneorganic silicon compound of formula (I) selected from the group of(3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane andadditionally comprising at least one organic silicon compound of formula(IV) selected from the group of methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,hexyltrimethoxysilane and hexyltriethoxysilane.

In a further preferred embodiment, the agent (a) comprises—based on thetotal weight of the agent (a):

-   -   0.5 to 5% by weight % of at least one first organic silicon        compound (a1) which is selected from the group of        (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,        (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane,        (3-dimethylaminopropyl)trimethoxysilane,        (3-dimethylaminopropyl)triethoxysilane        (2-dimethylaminoethyl)trimethoxysilane and        (2-dimethylaminoethyl)triethoxysilane, and    -   3.2 to 10 wt. % of at least one second organic silicon compound        (a1) selected from the group of methyltrimethoxysilane,        methyltriethoxysilane, ethyltrimethoxysilane,        ethyltriethoxysilane, propyltrimethoxysilane,        propyltriethoxysilane, hexyltrimethoxysilane,        hexyltriethoxysilane, octyltrimethoxysilane,        octyltriethoxysilane, dodecyltrimethoxysilane and        dodecyltriethoxysilane.

In this embodiment, the agent (a) comprises one or more organic siliconcompounds of a first group in a total amount of 0.5 to 3% by weight. Theorganic silicon compounds of this first group are selected from thegroup of (3-aminopropyl)trimethoxysilane,(3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane,(2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane,(3-dimethylaminopropyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane and/or(2-dimethylaminoethyl)triethoxysilane.

In this embodiment, the agent (a) comprises one or more organic siliconcompounds of a second group in a total amount of 3.2 to 10 wt. %. Theorganic silicon compounds of this second group are selected from thegroup of methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane,propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilaneand/or dodecyltriethoxysilane.

Even the addition of insignificant amounts of water leads to hydrolysisin organic silicon compounds with at least one hydrolysable group. Thehydrolysis products and/or organic silicon compounds having at least onehydroxy group may react with each other in a condensation reaction. Forthis reason, both the organosilicon compounds having at least onehydrolysable group and their hydrolysis and/or condensation products maybe present in the agent (a). When organosilicon compounds having atleast one hydroxyl group are used, both the organic silicon compoundshaving at least one hydroxyl group and their condensation products maybe present in the agent (a).

A condensation product is understood to be a product formed by thereaction of at least two organic silicon compounds each having at leastone hydroxyl group or hydrolysable group per molecule with eliminationof water and/or with elimination of an alkanol. The condensationproducts can be, for example, dimers, but also trimers or oligomers,with the condensation products being in equilibrium with the monomers.Depending on the amount of water used or consumed in the hydrolysis, theequilibrium shifts from monomeric organic silicon compounds tocondensation product.

Particularly satisfactory results were obtained when organic siliconcompounds of formula (I) and/or (II) were used in the process. Since, aspreviously described, hydrolysis/condensation already starts at tracesof moisture, the hydrolysis and/or condensation products of the organicsilicon compounds (I) and/or (II) are also included in this embodiment.

Color-Forming Compounds (a2)

When agent (a) is applied to the keratinous material, the organicsilicon compound(s) (a1) comprising one or more hydroxyl groups orhydrolysable groups per molecule are first hydrolyzed and oligomerizedor polymerized in the presence of the water. The hydrolysis products oroligomers formed in this way have a particularly high affinity for thesurface of the keratinous material. The simultaneous presence of thecoloring compounds (a2) in the agent (a) integrates them into theresulting oligomers or polymers to form a colored film on the keratinousmaterial. Following the application of agent (a), agent (b) is nowapplied. The successive application of agents (a) and (b) thus producesa coloration that is particularly resistant to external influences. Thecolorant compounds entrapped in these resistant films exhibit good washfastness.

As an essential component (a2) of the present disclosure, the agent (a)used in the dyeing process therefore comprises at least onecolor-imparting compound. The at least one colorant compound (a2)comprises at least one effect pigment comprising α) a substrate plateletand β) a coating, wherein the coating has at least one layer that is

(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigments.

The effect pigments are colored by the presence of a coloring compound(ii) from the group of pigments in the at least one layer.

Accordingly, with the help of the “colored” effect pigments, keratinfibers can be dyed in particularly intensive and numerous color shades.

The effect pigment has a substrate platelet.

The substrate wafer preferably has an average thickness of at most 150nm, preferably less than 50 nm, more preferably less than 30 nm,particularly preferably at most 25 nm, for example at most 20 nm. Theaverage thickness of the substrate platelets is at least 1 nm,preferably at least 2.5 nm, particularly preferably at least 5 nm, forexample at least 10 nm. Preferred ranges for substrate wafer thicknessare 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20nm, and 10 to 20 nm. Preferably, each substrate plate has a thicknessthat is as uniform as possible.

The substrate plate is preferably monolithic. Monolithic in this contextmeans comprising a single self-included unit without fractures,stratifications or inclusions, although microstructural changes mayoccur within the substrate platelet. The substrate platelet ispreferably homogeneous in structure, i.e., no concentration gradientoccurs within the platelet. In particular, the substrate platelet is notlayered and does not have particles or particulates distributed therein.

The size of the substrate platelet can be tailored to the specificapplication, for example the desired effect on a keratinous material.Typically, the substrate platelets have an average largest diameter ofabout 2 to 200 μm, especially about 5 to 100 μm.

In a preferred embodiment, the shape factor (aspect ratio), expressed bythe ratio of the average size to the average thickness, is at least 80,preferably at least 200, more preferably at least 500, particularlypreferably more than 750. The average size of the uncoated substrateplatelets is the d50 value of the uncoated substrate platelets. Unlessotherwise stated, the d50 value was determined using a Sympatec Helosdevice with QUIXEL wet dispersion. To prepare the sample, the sample tobe analyzed was pre-dispersed in isopropanol for 3 minutes.

The substrate platelet can be composed of any material that can beformed into platelet shape.

They can be of natural origin, but also synthetically produced.Materials from which the substrate platelets can be constructed includemetals and metal alloys, metal oxides, preferably aluminum oxide,inorganic compounds and minerals such as mica and (semi-)preciousstones, and plastics. Preferably, the substrate plates are constructedof a metal or alloy.

Any metal suitable for effect pigments can be used. Such metals includeiron and steel, as well as all air- and water-resistant (semi)metalssuch as platinum, tin, zinc, chromium, molybdenum and silicon, as wellas their alloys such as aluminum bronzes and brass. Preferred metals arealuminum, copper, silver and gold. Preferred substrate platelets includealuminum platelets and brass platelets, with aluminum substrateplatelets being particularly preferred.

Substrate plates made of aluminum can be produced, among other things,by punching out of aluminum foil or according to common milling andatomization techniques. For example, aluminum flakes are available fromthe Hall process, a wet milling process.

Other metal flakes, for example of bronze, can be obtained in a drygrinding process such as the Hametag process.

The substrate plates can have different shapes. For example, lamellar orlenticular metal platelets or so-called vacuum metallized pigments (VMP)can be used as substrate platelets. Lamellar substrate platelets areexemplified by an irregularly structured edge and are also referred toas “cornflakes” due to their appearance. Lenticular substrate flakeshave a regular round edge and are also known as “silverdollars” becauseof their appearance.

The metal or metal alloy substrate plates can be passivated, for exampleby anodizing (oxide layer) or chromating.

A coating can change the surface properties and/or optical properties ofthe effect pigment and increase the mechanical and chemical load-bearingcapacity of the effect pigments. For example, only the upper and/orlower side of the substrate wafer may be coated, with the side surfacesbeing recessed. Preferably, the entire surface of the optionallypassivated substrate platelets, including the side surfaces, is coveredby the layer. The substrate platelets are preferably completely encasedby the coating.

The coating may include one or more layers. In a preferred embodiment,the coating has only layer A. In a likewise preferred embodiment, thecoating has a total of at least two, preferably two or three, layers. Itmay be preferred to have the coating have two layers A and B, with layerB being different from layer A. Preferably, layer A is located betweenlayer B and the surface of the substrate plate. In yet another preferredembodiment, the coating has three layers A, B and C. In this embodiment,layer A is located between layer B and the surface of the substratewafer and layer C is located on top of layer B, which is different fromthe layer B below.

Suitable materials for layers A and, if necessary, B and C are allsubstances that can be permanently applied to the substrate platelets.The materials should preferably be applicable in film form. Preferably,the entire surface of the optionally passivated substrate platelets,including the side surfaces, is enveloped by layer A or by layers A andB or by layers A, B and C.

It is preferred that the metal oxide and/or metal oxide hydrate (i) isselected from the group of silicon (di)oxide, silicon oxide hydrate,aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide,manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromiumoxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide,zinc oxide and mixtures thereof.

Layer A preferably has at least one low refractive index metal oxideand/or metal oxide hydrate. Preferably, layer A comprises at least 95%by weight of low refractive index metal oxide (hydrate). Low refractiveindex materials have a refractive index of 1.8 or less, preferably 1.6or less.

Low refractive index metal oxides suitable for Layer A include, forexample, silicon (di)oxide, silicon oxide hydrate, aluminum oxide,aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide,magnesium oxide, and mixtures thereof, with silicon dioxide beingpreferred. Layer A preferably has a thickness of 1 to 100 nm,particularly preferably 5 to 50 nm, especially preferably 5 to 20 nm.

Layer B, if present, is different from Layer A and may contain at leastone highly refractive metal oxide. Highly refractive materials have arefractive index of at least 1.9, preferably at least 2.0, and morepreferably at least 2.4. Preferably, layer B comprises at least 95 wt.%, more preferably at least 99 wt. %, of high refractive index metaloxide(s).

If the layer B comprises a (highly refractive) metal oxide, itpreferably has a thickness of at least 50 nm. Preferably, the thicknessof layer B is no more than 400 nm, more preferably no more than 300 nm.

Highly refractive metal oxides suitable for layer B are, for example,selectively light-absorbing (i.e., colored) metal oxides, such asiron(III) oxide (α- and γ-Fe2O3, red), cobalt(II) oxide (blue),chromium(III) oxide (green), titanium(III) oxide (blue, usually presentin admixture with titanium oxynitrides and titanium nitrides), andvanadium(V) oxide (orange), as well as mixtures thereof. Colorlesshigh-index oxides such as titanium dioxide and/or zirconium oxide arealso suitable.

Layer B can contain a selectively absorbing dye in addition to a highlyrefractive metal oxide, preferably 0.001 to 5% by weight, particularlypreferably 0.01 to 1% by weight, in each case based on the total amountof layer B. Suitable dyes are organic and inorganic dyes that can bestably incorporated into a metal oxide coating. Dyes in the sense of thepresent disclosure have a solubility in water (760 mmHg) at 25° C. ofmore than 0.5 g/L and are therefore not to be regarded as pigments.

Alternatively, to a metal oxide, layer B may comprise a metal particlecarrier layer with metal particles deposited on the surface of the metalparticle carrier layer. In a preferred embodiment, the metal particlesdirectly cover a portion of the metal particle carrier layer. In thisembodiment, the effect pigment has areas in which there are no metalparticles, i.e., areas which are not covered with the metal particles.

The metal particle carrier layer comprises a metal layer and/or a metaloxide layer.

If the metal particle carrier layer comprises a metal layer and a metaloxide layer, the arrangement of these layers is not limited.

It is preferred that the metal particle support layer at least comprisesa metal layer. It is further preferred that the metal layer comprises anelement selected from tin (Sn), palladium (Pd), platinum (Pt) and gold(Au).

The metal layer can be formed, for example, by adding alkali to a metalsalt solution comprising the metal.

If the metal particle carrier layer comprises a metal oxide layer, thispreferably does not comprise silicon dioxide. The metal oxide layerpreferably comprises an oxide of at least one element selected from thegroup of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel),Fe (iron), Zr (zirconium), Ti (titanium) and Ce (cerium). Particularlypreferably, the metal particle support layer iii) in the form of a metaloxide layer comprises a metal oxide of Sn, Zn, Ti and Ce.

The metal particle support layer in the form of a metal oxide layer canbe produced, for example, by hydrolysis of an alkoxide of a metalforming the metal of the metal oxide in a sol-gel process.

The thickness of the metal particle support layer is preferably not morethan 30 nm and more preferably in the range of 0.1 to 10 nm.

The metal particles may comprise at least one element selected from thegroup of aluninuim (Al), titaniumn (Ti), chromium (Cr), iron (Fe),cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru),rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold(Au), and alloys thereof. It is particularly preferred that the metalparticles comprise at least one element selected from copper (Cu),nickel (Ni) and silver (Ag).

The average particle diameter of the metal particles is preferably notmore than 50 nm, more preferably not more than 30 nm. The distancebetween the metal particles is preferably not more than 10 nm.

Suitable methods for forming the metal particles include vacuumevaporation, sputtering, chemical vapor deposition (CVD), electrolessplating, or the like. Of these processes, electroless plating isparticularly preferred.

According to a preferred embodiment, the effect pigments have a furtherlayer C, comprising a metal oxide (hydrate), which is different from thelayer B underneath. Suitable metal oxides include silicon (di)oxide,silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zincoxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide,and chromium (III) oxide. Silicon dioxide is preferred.

The layer C preferably has a thickness of 10 to 500 nm, more preferably50 to 300 nm.

The coating of the effect pigment has at least one layer which, inaddition to the metal oxide and/or the metal oxide hydrate, furthercomprises a color-imparting compound (ii) from the group of pigments.

The at least one layer comprising (i) a metal oxide and/or metal oxidehydrate and (ii) a coloring compound selected from the group of pigmentsmay be layer A, B and/or C. In the case that the coating has only onelayer A, layer A also comprises the coloring compound (ii) from thegroup of pigments.

In the case where the coating of the effect pigment has two layers A andB and each comprises a metal oxide (hydrate), both layers A and B oronly one of the two layers may comprise the color-imparting compound(ii) from the group of pigments. Preferably, layer A comprises thecoloring compound (ii) from the group of pigments.

In the case where the coating has layers A, B and C and each comprises ametal oxide (hydrate), each of the layers A, B and C may contain acoloring compound (ii) selected from the group of pigments.Alternatively, in this embodiment, two of the three layers may containthe colorant compound (ii) selected from the group of pigments.Accordingly, the coloring compound (ii) may be from the group ofpigments in layer A and B, in layer A and C or in layer B and C.Likewise, only one of the three layers may comprise a coloring compound(ii) from the group of pigments. Accordingly, the coloring compound (ii)may be from the group of pigments in layer A, B or C. In a particularlypreferred embodiment of an effect pigment comprising a coating withlayers A, B and C, the coloring compound (ii) is from the group ofpigments in layer A and/or C.

In the case where the coating comprises layers A, B and C, layers A andC comprise a metal oxide (hydrate) and layer B comprises a metal layerhaving metal particles deposited thereon, each of layers A and C maycontain a coloring compound (ii) selected from the group of pigments.Alternatively, in this embodiment, only one of the layers A and C maycontain the coloring compound (ii) from the group of pigments.

In a particularly preferred embodiment of an effect pigment comprising acoating with layers A, B and C, the coloring compound (ii) is from thegroup of pigments in layer A and/or C.

It is particularly preferred that the effect pigment comprises asubstrate platelet of aluminum and a layer A comprising silica. If theeffect pigment based on a substrate platelet has a layer A and a layerC, it is preferred that the effect pigment has a substrate platelet ofaluminum and layers A and C comprising silica.

The at least one layer of the effect pigment has a color-impartingcompound (ii) from the group of pigments.

Pigments within the meaning of the present disclosure are coloringcompounds which have a solubility in water at 25° C. of less than 0.5g/L, preferably less than 0.1 g/L, even more preferably less than 0.05g/L. Water solubility can be determined, for example, by the methoddescribed below: 0.5 g of the pigment are weighed in a beaker. Astir-fish is added. Then one liter of distilled water is added. Thismixture is heated to 25° C. for one hour while stirring on a magneticstirrer. If undissolved components of the pigment are still visible inthe mixture after this period, the solubility of the pigment is below0.5 g/L. If the pigment-water mixture cannot be assessed visually due tothe high intensity of the finely dispersed pigment, the mixture isfiltered. If a proportion of undissolved pigments remains on the filterpaper, the solubility of the pigment is below 0.5 g/L.

Suitable pigments can be of inorganic and/or organic origin.

In a preferred embodiment, the effect pigment comprises at least onecolor-imparting compound (ii) selected from the group of inorganicand/or organic pigments.

Preferred pigments are selected from synthetic or natural inorganicpigments. Inorganic pigments of natural origin can be produced, forexample, from chalk, ochre, umber, green earth, fired Terra di Siena orgraphite. Furthermore, black pigments such as iron oxide black, coloredpigments such as ultramarine or iron oxide red, and fluorescent orphosphorescent pigments can be used as inorganic pigments.

Particularly suitable are colored metal oxides, hydroxides and oxidehydrates, mixed-phase pigments, sulfur-comprising silicates, silicates,metal sulfides, complex metal cyanides, metal sulphates, chromatesand/or molybdates. Particularly preferred pigments are black iron oxide(CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI77491), manganese violet (CI 77742), ultramarines (sodium aluminumsulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate(CI77289), iron blue (ferric ferrocyanide, CI77510) and/or carmine(cochineal).

Also particularly preferred pigments are colored pearlescent pigments.These are usually mica- and/or mica-based and can be coated with one ormore metal oxides. Mica belongs to the layer silicates. The mostimportant representatives of these silicates are muscovite, phlogopite,paragonite, biotite, lepidolite and margarite. To produce thepearlescent pigments in combination with metal oxides, the mica,muscovite or phlogopite, is coated with a metal oxide.

As an alternative to natural mica, synthetic mica coated with one ormore metal oxides can also be used as pearlescent pigment. Especiallypreferred pearlescent pigments are based on natural or synthetic mica(mica) and are coated with one or more of the metal oxides mentionedabove. The color of the respective pigments can be varied by varying thelayer thickness of the metal oxide(s).

Also preferred mica-based pigments are synthetically produced micaplatelets coated with metal oxide, based on synthetic fluorophlogopite(INCI: Synthetic Fluorphlogopite). The synthetic fluorophlogopiteplatelets are coated, for example, with tin oxide, iron oxide(s) and/ortitanium dioxide. The metal oxide layers may further contain pigmentssuch as ferric hexacyanidoferrate(II/III) or carmine red. Such micapigments are available, for example, under the name SYNCRYSTAL fromEckart.

Accordingly, a preferred effect pigment comprises at least one coloringcompound (ii) from the group of pigments selected from the group ofcolored metal oxides, metal hydroxides, metal oxide hydrates, silicates,metal sulfides, complex metal cyanides, metal sulfates, bronze pigmentsand/or from colored mica- or mica-based pigments coated with at leastone metal oxide and/or a metal oxychloride.

In a further preferred embodiment, the effect pigment comprises at leastone coloring compound (ii) from the group of pigments selected frommica- or mica-based pigments which are reacted with one or more metaloxides from the group comprising titanium dioxide (CI 77891), black ironoxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown ironoxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine(sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromiumoxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue(ferric ferrocyanide, CI 77510).

Other suitable pigments are based on metal oxide-coated platelet-shapedborosilicates. These are coated with tin oxide, iron oxide(s), silicondioxide and/or titanium dioxide, for example. Such borosilicate-basedpigments are available, for example, under the name MIRAGE from Eckartor Reflecks from BASF SE.

Examples of particularly suitable pigments are commercially availableunder the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron®from Merck, Ariabel® and Unipure® from Sensient, Prestige® from EckartCosmetic Colors, Flamenco®, Cellini®, Cloisonné®, Duocrome®, Gemtone®,Timica®, MultiReflections, Chione from BASF SE and Sunshine® fromSunstar.

Very particularly preferred pigments with the trade name Colorona® are,for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona PassionOrange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona PatinaSilver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470(CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA,TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona BlackstarBlue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple,Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491(IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona ImperialRed, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUMDIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold,Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRONOXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE,CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze,Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA,CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891(TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck,CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491(IRON OXIDES)

Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide),Silica, CI 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRONOXIDES, MICA, CI 77891, CI 77491 (EU)

Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891(Titanium dioxide)Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491(Iron oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Further particularly preferred pigments with the trade name Xirona® are,for example:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin OxideXirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica,Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide),Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (TitaniumDioxide), Tin Oxide.

In addition, particularly preferred pigments with the trade nameUnipure® are, for example:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica UnipureBlack LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure YellowLC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the effect pigment may also comprise one ormore color-imparting compounds (ii) selected from the group of organicpigments.

The organic pigments are correspondingly insoluble organic dyes orcolorants which may be selected, for example, from the group of nitroso,nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline,quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo,thioindido, dioxazine and/or triarylmethane compounds.

Examples of particularly suitable organic pigments are carmine,quinacridone, phthalocyanine, sorghum, blue pigments with the ColorIndex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments with the Color Index numbers CI 11680, CI 11710,CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005,green pigments with the Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with the Color Index numbers CI 11725, CI 15510,CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085,CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In another particularly preferred embodiment, the effect pigmentcomprises a coloring compound (ii) from the group of organic pigmentsselected from the group of carmine, quinacridone, phthalocyanine,sorghum, blue pigments having the color index numbers CI 42090, CI69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments havingthe color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with ColorIndex numbers CI 61565, CI 61570, CI 74260, orange pigments with ColorIndex numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments withColor Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI73360, CI 73915, CI 75470 and mixtures thereof.

The organic pigment can also be a color paint. As contemplated herein,the term color lacquer means particles comprising a layer of absorbeddyes, the unit of particle and dye being insoluble under the abovementioned conditions. The particles can, for example, be inorganicsubstrates, which can be aluminum, silica, calcium borosilicate, calciumaluminum borosilicate or even aluminum.

For example, alizarin color varnish can be used.

Also, suitable colorant compounds (ii) from the group of pigments areinorganic and/or organic pigments modified with a polymer. The polymermodification can, for example, increase the affinity of the pigments tothe respective material of the at least one layer.

The particle size of the colorant compound (ii) used depends on thelayer in which the colorant layer is present. The color-impartingcompound preferably has a particle size D₉₀, which is smaller than thelayer thickness of the at least one layer. More preferably, the particlesize D₉₅ of the coloring compound is smaller than the layer thickness ofthe at least one layer. Even more preferably, the particle size D₉₉ ofthe colorant compound is smaller than the layer thickness of the atleast one layer. Very preferably, the particle size D₁₀₀ of the coloringcompound is smaller than the layer thickness of the at least one layer.The particle size of the coloring compound can be determined using, forexample, dynamic light scattering (DLS) or static light scattering(SLS). D₉₀ means that 90% of the particles of the coloring compound aresmaller than the layer thickness of the at least one layer. Accordingly,D₉₅ means that 95% of the particles of the coloring compound are smallerthan the layer thickness of the at least one layer, etc.

The amount of color-imparting compound (ii) from the group of pigmentsin the at least one layer comprising

(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound selected from the group of pigments,is preferably up to 5% by weight, based on the total weight of thelayer.

Layers A and C serve as corrosion protection as well as chemical andphysical stabilization. Particularly preferably, layers A and C containsilicon dioxide or aluminum oxide applied by the sol-gel process.

The effect pigments based on coated substrate platelets preferably havea thickness of 70 to 500 nm, particularly preferably 100 to 400 nm,especially preferably 150 to 320 nm, for example 180 to 290 nm. The lowthickness of the coated substrate platelets is achieved by keeping thethickness of the uncoated substrate platelets low, but also by adjustingthe thicknesses of the coatings A and, if present, C to as small a valueas possible.

The adhesion and abrasion resistance of effect pigments comprising α) asubstrate platelet and β) a coating, wherein the coating has at leastone layer that is

(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigmentsin the keratinous material can be significantly increased byadditionally modifying the outermost layer, layer A, B or C depending onthe structure, with organic compounds such as silanes, phosphoric acidesters, titanates, borates or carboxylic acids. In this case, theorganic compounds are bonded to the surface of the outermost, preferablymetal oxide-comprising, layer A, B, or C. The outermost layer denotesthe layer that is spatially farthest from the substrate platelet. Theorganic compounds are preferably functional silane compounds that canbind to the metal oxide-comprising layer A, B, or C. These can be eithermono- or bifunctional compounds. Examples of bifunctional organiccompounds are methacryloxypropenyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane. 3-acryloxypropyltrimethoxysilane,2-acryloxyethyltrimethoxysilane, 3-methacryloxy-propyltriethoxysilane,3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane,2-acryloxyethyltriethoxysilane,3-methacryloxypropyltris(methoxyethoxy)silane,3-methacryloxypropyltris(butoxyethoxy)silane,3-methacryloxy-propyltris(propoxy)silane,3-methacryloxypropyltris(butoxy)silane,3-acryloxy-propyltris(methoxyethoxy)silane,3-acryloxypropyltris(butoxyethoxy)silane,3-acryl-oxypropyltris(butoxy)silane, vinyltrimethoxysilane,vinyltriethoxysilane, vinylethyl dichlorosilane,vinylmethyldiacetoxysilane, vinylmethyldichlorosilane,vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane,phenylvinyldiethoxysilane, or phenylallyldichlorosilane. Furthermore, amodification with a monofunctional silane, an alkylsilane or arylsilane,can be carried out. This has only one functional group covalently bondedto the surface of the effect pigment, which comprises a) a substrateplatelet and 3) a coating, wherein the coating has at least one layerthat is(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigments(i.e., to the outermost metal oxide (hydrate)-comprising layer) or, ifnot completely covered, to the metal surface. The hydrocarbon residue ofthe silane points away from the pigment. Depending on the type andnature of the hydrocarbon residue of the silane, a varying degree ofhydrophobicity of the pigment is achieved. Examples of such silanes arehexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularlypreferred are effect pigments based on silica-coated aluminum substrateplatelets surface-modified with a monofunctional silane.Octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilaneand hexadecyltriethoxysilane are particularly preferred. Due to thechanged surface properties/hydrophobization, an improvement can beachieved in terms of adhesion, abrasion resistance and alignment in theapplication.

It has been shown that effect pigments with such a surface modificationalso exhibit better compatibility with the organosilicon compounds usedand/or their condensation or polymerization products.

Particularly satisfactory results could be obtained if the agent(a)—based on the total weight of the agent (a)—comprises one or moreeffect pigments in a total amount of 0.01 to 10% by weight, preferably0.1 to 8% by weight, more preferably 0.2 to 6% by weight and verypreferably 0.5 to 4.5% by weight.

In addition to the effect pigment, the agent (a) may comprise furthercolorant compounds (a2) selected from the group of pigments and/ordirect dyes.

The use of pigments has proved to be particularly preferable in thiscontext.

In another very particularly preferred embodiment, the agent (a)comprises at least one further colorant compound (a2) from the group ofpigments.

The pigments which can be used as further colorant compound (a2) fromthe group of pigments correspond to the pigments already described aboveas colorant compound (ii).

In a preferred embodiment, agent (a) comprises at least one furthercolor-imparting compound (a2) from the group of inorganic and/or organicpigments.

In a further preferred embodiment, agent (a) comprises at least onefurther colorant compound (a2) from the group of inorganic pigmentsselected from the group of colored metal oxides, metal hydroxides, metaloxide hydrates, silicates, metal sulfides, complex metal cyanides, metalsulfates, bronze pigments and/or from colored mica- or mica-basedpigments coated with at least one metal oxide and/or a metaloxychloride.

In a further preferred embodiment, agent (a) comprises at least onefurther colorant compound (a2) from the group of pigments selected frommica- or mica-based pigments which are reacted with one or more metaloxides from the group comprising titanium dioxide (CI 77891), black ironoxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown ironoxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine(sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromiumoxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue(ferric ferrocyanide, CI 77510).

Other effect pigments, such as metallic luster pigments, can be used.

The effect pigments may include, for example, pigments based on alamellar substrate platelet, pigments based on lenticular substrateplatelets, pigments based on substrate platelets comprising “vacuummetallized pigments” (VMP).

Suitable effect pigments include, for example, the pigments Alegrace®Marvelous, Alegrace© Gorgeous or Alegrace® Aurous from Schlenk MetallicPigments.

Also, suitable effect pigments are the aluminum-based pigments of theSILVERDREAM series and the pigments of the VISIONAIRE series fromEckart, which are based on aluminum or on copper/zinc-comprising metalalloys.

Other suitable effect pigments are the aluminum-based pigments of theCosmicolor® series from Toyal Europe. Particularly suitable effectpigments are the colored effect pigments Cosmicolor® Celeste.

Other suitable effect pigments are based on metal oxide-coatedplatelet-shaped borosilicates. These are coated with tin oxide, ironoxide(s), silicon dioxide and/or titanium dioxide, for example. Suchborosilicate-based pigments are available, for example, under the nameMIRAGE from Eckart or Reflecks from BASF SE.

In a further embodiment of the process, the agent (a) may also compriseone or more colorant compounds selected from the group of organicpigments.

In another particularly preferred embodiment, the agent (a) comprises atleast one further colorant compound (a2) from the group of organicpigments selected from the group of carmine, quinacridone,phthalocyanine, sorghum, blue pigments having the color index numbers CI42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigmentshaving the color index numbers CI 11680, CI 11710, CI 15985, CI 19140,CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments withColor Index numbers CI 61565, CI 61570, CI 74260, orange pigments withColor Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigmentswith the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI58000, CI 73360, CI 73915 and/or CI 75470.

Due to their excellent light and temperature stability, the use of theabove pigments in agent (a) is particularly preferred. It is alsopreferred if the pigments used have a certain particle size. Thisparticle size leads on the one hand to an even distribution of thepigments in the formed polymer film and on the other hand avoids a roughhair or skin feeling after application of the cosmetic product. Ascontemplated herein, it is therefore advantageous if the at least onepigment has an average particle size D₅₀ of 1 to 50 μm, preferably 5 to45 μm, preferably 10 to 40 μm, 14 to 30 μm. The mean particle size D₅₀,for example, can be determined using dynamic light scattering (DLS).

In addition to the effect pigment, the agent (a) may contain as furthercolorant compound(s) (a2) other effect pigments such as pigments, basedon lamellar substrate platelets and/or pigments based on VMP substrateplatelets. VMP refers to vacuum metallized pigments.

In a further preferred embodiment, agent (a) comprises—based on thetotal weight of the agent (a)—one or more further colorant compound(s)(a2) in the form of pigments in a total amount of from 0.01 to 10% byweight, preferably from 0.1 to 8% by weight, more preferably from 0.2 to6% by weight and very particularly preferably from 0.5 to 4.5% byweight.

As further colorant compound(s) (a2), the agents (a) used in the processmay also contain one or more direct dyes. Direct-acting dyes are dyesthat draw directly onto the hair and do not require an oxidative processto form the color. Direct dyes are usually nitrophenylene diamines,nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes orindophenols.

The direct dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments.

Preferably, the direct dyes within the meaning of the present disclosurehave a solubility in water (760 mmHg) at 25° C. of more than 1 g/L.

Direct dyes can be divided into anionic, cationic and non-ionic directdyes.

In a further preferred embodiment, agent (a) comprises at least oneanionic, cationic and/or nonionic direct dye as further coloringcompound (a2).

In a further preferred embodiment, agent (a) comprises at least onefurther colorant compound (a2) from the group comprising anionic,nonionic, and/or cationic direct dyes.

Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, BasicViolet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue No. 16, BasicBlue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow87, Basic Orange 31, Basic Red 51 Basic Red 76

As non-ionic direct dyes, non-ionic nitro and quinone dyes and neutralazo dyes can be used. Suitable non-ionic direct dyestuffs are thoselisted under the international designations or Trade names HC Yellow 2,HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1,Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13,HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 knowncompounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)-aminophenol2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-4-nitrophenol.

In the course of the work leading to the present disclosure, it has beenfound that dyeing's of particularly high color intensity can be producedwith agents (a) comprising at least one anionic direct dye.

In an explicitly quite particularly preferred embodiment, the agent (a)further comprises at least one anionic direct dye as a further colorantcompound (a2).

Anionic direct dyes are also called acid dyes. Acid dyes are direct dyesthat have at least one carboxylic acid group (—COOH) and/or onesulphonic acid group (—SO₃H). Depending on the pH value, the protonatedforms (—COOH, —SO₃H) of the carboxylic acid or sulphonic acid groups arein equilibrium with their deprotonated forms (—COO—, —SO₃; present). Theproportion of protonated forms increases with decreasing pH. If directdyes are used in the form of their salts, the carboxylic acid groups orsulphonic acid groups are present in deprotonated form and areneutralized with corresponding stoichiometric equivalents of cations tomaintain electro neutrality. The acid dyes can also be used in the formof their sodium salts and/or their potassium salts.

The acid dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments. Preferably the acid dyeswithin the meaning of the present disclosure have a solubility in water(760 mmHg) at 25° C. of more than 1 g/L.

The alkaline earth salts (such as calcium salts and magnesium salts) oraluminum salts of acid dyes often have a lower solubility than thecorresponding alkali salts. If the solubility of these salts is below0.5 g/L (25° C., 760 mmHg), they do not fall under the definition of adirect dye.

An essential characteristic of acid dyes is their ability to formanionic charges, whereby the carboxylic acid or sulphonic acid groupsresponsible for this are usually linked to different chromophoricsystems. Suitable chromophoric systems can be found, for example, in thestructures of nitrophenylenediamines, nitroaminophenols, azo dyes,anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes,oxazine dyes and/or indophenol dyes.

In the context of one embodiment, a process for dyeing keratinousmaterial is thus preferred, wherein the agent (a) further comprises atleast one anionic direct dye as further coloring compound (a2), which isselected from the group of the nitrophenylenediamines, thenitroaminophenols, the azo dyes, the anthraquinone dyes, thetriarylmethane dyes, the xanthene dyes, the rhodamine dyes, the oxazinedyes and/or the indophenol dyes, of the triarylmethane dyes, of thexanthene dyes, of the rhodamine dyes, of the oxazine dyes and/or of theindophenol dyes, the dyes from the abovementioned group each comprisingat least one carboxylic acid group (—COOH), a sodium carboxylate group(—COONa), a potassium carboxylate group (—COOK), a sulfonic acid group(—SO₃H), a sodium sulfonate group (—SO₃Na) and/or a potassium sulfonategroup (—SO₃K).

For example, one or more compounds from the following group can beselected as particularly well suited acid dyes: Acid Yellow 1 (D&CYellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316,COLIPA no B001), Acid Yellow 3 (COLIPA no: C 54, D&C Yellow No 10,Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), AcidYellow 17 (CI 18965), Acid Yellow 23 (COLIPA no C 29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), AcidYellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7(2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA no C015),Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), AcidOrange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No. 201;RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No. 1),Acid Red 14 (C.I.14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red27 (E 123, CI 16185, C-Rot 46, Real red D, FD&C Red Nr.2, Food Red 9,Naphthol red S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI17200), Acid Red 35 (CI C.I.18065), Acid Red 51 (CI 45430, Pyrosin B,Tetraiodfluorescein, Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red106, Solar Rhodamine B, Acid Rhodamine B, Red no 106 Pontacyl BrilliantPink), Acid Red 73 (CI CI 27290), Acid Red 87 (Eosin, CI 45380), AcidRed 92 (COLIPA no C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, AcidViolet 43 (Jarocol Violet 43, Ext. D&C Violet no 2, C.I. 60730, COLIPAno C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), AcidBlue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blue V, CI 42051),Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133,Patent Blue AE, Amido blue AE, Erioglaucin A, CI 42090, C.I. Food Blue2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI42095), Acid Green 9 (C.I.42100), Acid Green 22 (C.I.42170), Acid Green25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50(Brilliant Acid Green BS, C.I. 44090, Acid Brilliant Green BS, E 142),Acid Black 1 (Black no 401, Naphthalene Black 10B, Amido Black 10B, CI20 470, COLIPA no B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&COrange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&CBrown 1.

For example, the water solubility of anionic direct dyes can bedetermined in the following way. 0.1 g of the anionic direct dye isplaced in a beaker. A stir-fish is added. Then add 100 ml of water. Thismixture is heated to 25° C. on a magnetic stirrer while stirring. It isstirred for 60 minutes. The aqueous mixture is then visually assessed.If there are still undissolved residues, the amount of water isincreased—for example in steps of 10 ml. Water is added until the amountof dye used is completely dissolved. If the dye-water mixture cannot beassessed visually due to the high intensity of the dye, the mixture isfiltered. If a proportion of undissolved dyes remains on the filterpaper, the solubility test is repeated with a higher quantity of water.If 0.1 g of the anionic direct dye dissolves in 100 ml water at 25° C.,the solubility of the dye is 1 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic aciddisodium salt and has a solubility in water of at least 40 g/L (25° C.).

Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonicacids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a watersolubility of 20 g/L (25° C.).Acid Yellow 9 is the disodium salt of8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility inwater is above 40 g/L (25° C.).Acid Yellow 23 is the trisodium salt of4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylicacid and is highly soluble in water at 25° C.Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulphonate. Its water solubility is more than 7 g/L (25° C.).Acid Red 18 is the trisodium salt of7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonateand has an extremely high water solubility of more than 20% by weight.Acid Red 33 is the disodium salt of5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, itssolubility in water is 2.5 g/L (25° C.).Acid Red 92 is the disodium salt of3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoicacid, whose solubility in water is indicated as greater than 10 g/L (25°C.).Acid Blue 9 is the disodium salt of2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonateand has a solubility in water of more than 20% by weight (25° C.).

In a highly preferred process the agent (a) comprises at least onefurther colorant compound (a2) from the group of anionic direct dyesselected from the group of Acid Yellow 1, acid yellow 3, acid yellow 9,acid yellow 17, acid yellow 23, acid yellow 36, acid yellow 121, acidorange 6, acid orange 7, acid orange 10, acid orange 11, acid orange 15,acid orange 20, acid orange 24, acid red 14, acid red 27, acid red 33,acid red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, AcidRed 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, AcidViolet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, AcidBlue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, AcidGreen 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, AcidGreen 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&CYellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

The direct dye(s), in particular the anionic direct dyes, can be used indifferent amounts in the agent (a) depending on the desired colorintensity. Particularly satisfactory results were obtained when theagent (a) comprises—based on its total weight—one or more direct dyes asa further coloring compound (a2) in a total amount of from 0.01 to 10%by weight, preferably from 0.1 to 8% by weight, more preferably from 0.2to 6% by weight and very particularly preferably from 0.5 to 4.5% byweight.

In a further preferred embodiment, agent (a)—based on the total weightof the agent (a)—further comprises one or more direct dyes as furthercolorant compound (a2) in a total amount of from 0.01 to 10% by weight,preferably from 0.1 to 8% by weight, more preferably from 0.2 to 6% byweight and very preferably from 0.5 to 4.5% by weight.

Silicone Polymers (a3)

In another very particularly preferred embodiment, the agent (a) used inthe process additionally comprises at least one silicone polymer (a3).

Silicone polymers, which can alternatively be called silicones forshort, are understood to be poly(organo)siloxanes. Silicone polymers area group of synthetic polymers in which silicon atoms are linked viaoxygen atoms.

Silicone polymers are macromolecules with a molecular weight of at least500 g/mol, preferably at least 1000 g/mol, more preferably at least 2500g/mol, particularly preferably at least 5000 g/mol, which compriserepeating organic units.

The maximum molecular weight of the silicone polymer depends on thedegree of polymerization (number of polymerized monomers) and the batchsize and is partly determined by the polymerization method. For thepurposes of the present disclosure, it is preferred if the maximummolecular weight of the silicone polymer is not more than 107 g/mol,preferably not more than 10⁶ g/mol, and particularly preferably not morethan 10⁵ g/mol.

The silicone polymers comprise many Si—O repeating units, and the Siatoms may carry organic radicals such as alkyl groups or substitutedalkyl groups.

Corresponding to the high molecular weight of silicone polymers, theseare based on more than 10 Si—O repeat units, preferably more than 50Si—O repeat units, and more preferably more than 100 Si—O repeat units,most preferably more than 500 Si—O repeat units.

The silicone polymers (a3) included in agent (a) are therefore differentfrom the silanes (a1) also included in agent (a).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, wherein the agent comprises (a):

(a3) at least one silicone polymer.

In the work leading to the present disclosure, it was found thatincorporation of the silicone polymer (a3) into the agent (a) resultedin an improvement in hair feel.

The film produced by the oligomerization or polymerization of theorganosilicon compounds (silanes) (a1) may exhibit a certain stickinessor even softness, especially when higher amounts of silanes (a1) areused, which may have a detrimental effect on the feel of the keratinicmaterials on the one hand and on the durability of the film on theother. Without being committed to this theory, it is believed that thejoint application of the silane (a1) and the silicone polymer (a3) inthe agent (a) leads to a reaction or interaction of the two componentswith each other. When silane and silicone polymer are used together, thesilanes form a film, as previously described, into which the siliconepolymers are either incorporated, or to which the silicone polymersagglomerate. It has been found that the film formed in this way is muchmore supple, flexible, durable and less brittle.

Accordingly, it was observed that the rheological properties of the filmproduced by agent (a) could be improved by the addition of at least onesilicone polymer (a3). In the presence of the silicone polymers (a3),the film became firmer or more rigid, leaving the colored keratinousmaterials with a less sticky, smoother, and more pleasing appearance.Furthermore, the higher strength of the film also had positive effectson the fastness properties of the keratinic materials, especially ontheir rub fastness properties. Since the dyed films were more resistantwhen in contact with combs, brushes and textiles, they showed lessabrasion when in contact with these items.

When certain silicone polymers (a3) were used, the advantages describedabove were particularly pronounced. It has therefore been found to beparticularly preferred if the agents (a) used in the process contain atleast one alkoxy-modified silicone polymer and/or at least oneamino-modified silicone polymer (a3).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, wherein the agent comprises (a):

(a3) at least one alkoxy-modified and/or amino-modified siliconepolymer.

In another preferred embodiment, the agent (a) comprises at least onealkoxy-modified silicone polymer.

Alkoxy-modified silicones are silicones whose structure includes atleast one structural alkoxy unit. This structural alkoxy unit can be,for example, an alkoxy group. Alkoxy groups are understood to be C₂-C₁₀alkoxy groups. The alkoxy group may be terminal to the silicone (i.e.,present, for example, as the group —O—CH₃ or as the group —O—CH₂—CH₃).However, it is equally as contemplated herein if the alkoxy group itselfstill carries a substituent; in this case, an alkoxy modification isunderstood to be at least one grouping located on the silicone such as,for example, (—CH₂—CH₂—O—), (—CH₂—CH₂—CH₂—O—), (—CH(CH₃)—CH₂—O—),(—CH₂—CH(CH₃)—CH₂—O—) or (—CH₂—CH₂—CH₂—CH₂—O—). Preferably, thealkoxy-modified silicones (A) carry at least one grouping (—CH₂—CH₂—O—)and/or (—CH₂—CH₂—CH₂—O—).

The alkoxy groups may be linked to the silicone either via a carbon atomor via an oxygen atom, for example, the silicones may bear thestructural units of the formula (S-a), (S-b), (S-c) and/or (S-d):

It is particularly preferred if the alkoxy-modified silicone polymer(s)(a3) carry more than one alkoxy group, i.e., if the silicone polymers(a3) are poly alkoxylated. Polyalkoxylated silicones carry as structuralunits polyoxyalkylene groups, polyoxyethylene groups (i.e., groups ofthe type [—CH2-CH2-O—]_(m)) and/or poloxypropylene groups (i.e., groupsof the type [—CH(CH3)-CH2-O—]_(m) and/or [—CH2-CH2-CH2-O—]_(m)).Preferably, the number of polyoxyalkylene units in the silicone polymeris at least 2. Therefore, m is an integer greater than or equal to 2.

Particularly preferably, the alkoxy-modified silicone (a3) is a nonionicsilicone. Non-ionic silicones carry neither positive nor negativecharges.

Very particularly suitable polyalkoxylated silicones (a3) comprise atleast one structural unit of the formula (S-I)

whereinn is an integer from 2 to 20, preferably an integer from 4 to 18, morepreferably an integer from 6 to 16, still more preferably an integerfrom 8 to 14, and most preferably the number 12.

The positions marked with an asterisk * in the above formulas representthe free valences of the corresponding bonds, whereby the bond can be toa further Si atom, a further O atom and/or a further C atom.

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, wherein the agent comprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of formula (S-I)

-   -   wherein        -   n is an integer from 2 to 20, preferably an integer from 4            to 18, more preferably an integer from 6 to 16, still more            preferably an integer from 8 to 14, and most preferably the            number 12.

A preferred alkoxy-modified silicone polymer (a3) may contain, inaddition to one or more structural units of the general formula (S-I),further structural units that differ structurally from the units offormula (S-I). Particularly preferably, the alkoxy-modified siliconepolymer additionally comprises one or more dimethylsiloxane units.Depending on whether the silicone is linear or branched, it has two (inthe case of a chain linear silicone) or more (in the case of a branchedsilicone) end groups. It has been found to be particularly advantageousif a silicone polymer (a3) has a trimethylsilyloxy group (i.e., a group—O—Si(CH₃)₃) as end groups in each case.

In a further particularly preferred embodiment, agent (a) comprises atleast one silicone polymer (a3) which is composed of structural units ofthe formula (S-I), the formula (S-II), the formula (S-III) and theformula (S-IV),

wherein n—independently in each structural unit (S-I)—represents in eachcase an integer from 2 to 20, preferably an integer from 4 to 18, morepreferably an integer from 6 to 16, still more preferably an integerfrom 8 to 14, and most preferably the number 12.

A silicone polymer (a3) composed of structural units of the formula(S-I), the formula (S-II), the formula (S-III) and the formula (S-IV) isunderstood in this context to mean a silicone which exclusivelypossesses (in each case one or more) structural units of the formulae(S-I), (S-II), (S-III) and (S-IV). Here, the silicone can also containdifferent structural units of the formula (S-I), each of which isdistinguished by its number n.

The positions marked with an asterisk in the structural units eachrepresent the linkage points to the other structural units. For example,a very particularly preferred silicone polymer (a3) composed ofstructural units of formula (S-I), formula (S-II), formula (S-III) andformula (S-IV) may have the following structure:

x and y are chosen here depending on the desired molecular weight of thesilicone, and n represents one of the preferred or particularlypreferred integers described above as contemplated herein.

Both low molecular weight and higher molecular weight alkoxy-modifiedsilicones can be used as silicone polymers (a3). Particularly beneficialeffects were observed for silicone polymers (a3) with a molar mass of800 to 10,000 g/mol, preferably of 1,000 to 9,000 g/mol, furtherpreferably of 2,000 to 8,000 g/mol and especially preferably of 2,500 to5,000 g/mol.

Particularly well-suited silicone polymers include:

Abil B 8843 from Evonik, PEG-14 DIMETHICONE

Xiameter OFX 0193 Fluid by the Company Dow Corning, PEG-12 Dimethicone

Furthermore, particularly satisfactory results were also obtained whenan agent (a) comprising an amino-modified silicone polymer (a3) was usedin the process. The amino-modified silicone polymer may alternatively bereferred to as an amino-functionalized silicone polymer or also as anaminosilicone.

In another preferred embodiment, the agent (a) comprises at least oneamino-modified silicone polymer.

Agent (a) may contain one or more different amino-modified siliconepolymers (a3). Such silicones can be exemplified, for example, by theformula (S-V)

M(R_(a)Q_(b)SiO_((4-a-b)/2)x)(R_(c)SiO_((4-c)/2)y)M  (S-V)

in which formula above R is a hydrocarbon or a hydrocarbon radicalhaving from 1 to about 6 carbon atoms, Q is a polar radical of thegeneral formula —R¹HZ wherein R¹ is a divalent linking group bonded tohydrogen and the radical Z composed of carbon and hydrogen atoms,carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogenatoms, and Z is an organic amino functional radical comprising at leastone amino functional group; “a” takes values ranging from about 0 toabout 2, “b” takes values ranging from about 1 to about 3, “a”+“b” isless than or equal to 3, and “c” is a number ranging from about 1 toabout 3, and x is a number ranging from 1 to about 2,000, preferablyfrom about 3 to about 50 and most preferably from about 3 to about 25,and y is a number in the range of from about 20 to about 10,000,preferably from about 125 to about 10,000 and most preferably from about150 to about 1,000, and M is a suitable silicone end group as known inthe prior art, preferably trimethylsiloxy. Non-limiting examples ofradicals represented by R include alkyl radicals, such as methyl, ethyl,propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl,isohexyl and the like; alkenyl radicals, such as vinyl, halovinyl,alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals, such ascyclobutyl, cyclopentyl, cyclohexyl and the like; phenyl radicals,benzyl radicals, halohydrocarbon radicals, such as 3-chloropropyl,4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl,chlorophenyl, and the like; and sulfur-comprising radicals, such asmercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl, and thelike; preferably R is an alkyl radical comprising from 1 to about 6carbon atoms, and most preferably R is methyl. Examples of R¹ includemethylene, ethylene, propylene, hexamethylene, decamethylene,—CH₂CH(CH₃)CH₂—, phenylene, naphthylene, —CH₂CH₂SCH₂CH₂—, —CH₂CH₂OCH₂—,—OCH₂CH₂—, —OCH₂ CH₂CH₂—, —CH₂CH(CH₃)C(O)OCH₂—, —(CH₂)₃CC(O)OCH₂CH₂—,—C₆H₄C₆H₄—, —C₆H₄CH₂C₆H₄—; and —(CH₂)₃C(O)SCH₂CH₂—.

Z is an organic amino functional residue comprising at least one aminofunctional group. One formula for Z is NH(CH₂)_(z)NH₂, where z is 1 ormore. Another formula for Z is —NH(CH₂)_(z)(CH₂)_(zz)NH, wherein both zand zz are independently 1 or more, this structure comprising diaminoring structures, such as piperazinyl. Z is most preferably an—NHCH₂CH₂NH₂ residue. Another formula for Z is —N(CH₂)_(z)(CH₂)_(zz)NX₂or —NX₂, wherein each X of X₂ is independently selected from the groupof hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine-functional radical of the formula—CH₂CH₂CH₂NHCH₂CH₂NH₂. In the formulas, “a” takes values ranging fromabout 0 to about 2, “b” takes values ranging from about 2 to about 3,“a”+“b” is less than or equal to 3, and “c” is a number ranging fromabout 1 to about 3. The molar ratio of R_(a)Q_(b)SiO_((4-a-b)/2) unitsto R_(c)SiO_((4-c)/2) units is in the range of about 1:2 to 1:65,preferably from about 1:5 to about 1:65 and most preferably by about1:15 to about 1:20. If one or more silicones of the above formula areused, then the various variable substituents in the above formula may bedifferent for the various silicone components present in the siliconeblend.

In a particularly preferred embodiment, an agent (a) is applied to thekeratinous material, wherein the agent (a) is an amino-modified siliconepolymer (a3) of formula (S-VI)

R′_(a)G_(3-a)-Si(OSiG₂)_(n)-(OSiG_(b)R′_(2-b))_(m)—O—SiG_(3-a)-R′_(a)  (S-VI),

wherein:

-   -   G is —H, a phenyl group, —OH, —O—CH₃, —CH₃, —O—CH₂CH₃, —CH₂CH₃,        —O—CH₂CH₂CH₃, —CH₂CH₂CH₃, —O—CH(CH₃)₂, —CH(CH₃)₂,        —O—CH₂CH₂CH₂CH₃, —CH₂CH₂CH₂CH₃, —O—CH₂CH(CH₃)₂, —CH₂CH(CH₃)₂,        —O—CH(CH₃)CH₂CH₃, —CH(CH₃)CH₂CH₃, —O—C(CH₃)₃, —C(CH₃)₃;    -   a stands for a number between 0 and 3, especially 0;    -   b stands for a number between 0 and 1, especially 1,    -   m and n are numbers whose sum (m+n) is between 1 and 2000,        preferably between 50 and 150, where n preferably assumes values        from 0 to 1999 and from 49 to 149 and m preferably assumes        values from 1 to 2000, from 1 to 10,    -   R′ is a monovalent radical selected from        -   -Q-N(R″)—CH₂—CH₂—N(R″)₂        -   -Q-N(R″)₂        -   -Q-N+(R″)₃A⁻        -   -Q-N+H(R″)₂A⁻        -   -Q-N⁺H₂(R″)A⁻        -   -Q-N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,            where each Q is a chemical bond, —CH₂—, —CH₂—CH₂—,            —CH₂CH₂CH₂—, —C(CH₃)₂—, —CH₂CH₂CH₂CH₂—, —CH₂C(CH₃)₂—,            —CH(CH₃)CH₂CH₂—,            R″ represents identical or different radicals selected from            the group of —H, -phenyl, -benzyl, —CH₂—CH(CH₃)Ph, the C₁₋₂₀            alkyl radicals, preferably —CH₃, —CH₂CH₃, —CH₂CH₂CH₃,            —CH(CH₃)₂, —CH₂CH₂CH₂H₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃,            —C(CH₃)₃, and A represents an anion preferably selected from            chloride, bromide, iodide or methosulfate.

In another preferred embodiment, an agent (a) is applied to thekeratinous material, wherein the agent (a) comprises at least oneamino-modified silicone polymer (a3) of formula (S-VII),

wherein m and n are numbers whose sum (m+n) is between 1 and 2000,preferably between 50 and 150, n preferably assuming values from 0 to1999 and from 49 to 149, and m preferably assuming values from 1 to2000, from 1 to 10.

According to the INCI declaration, these silicones are calledtrimethylsilylamodimethicones.

In another preferred embodiment, an agent (a) is applied to thekeratinous material, wherein the agent (a) comprises at least oneamino-modified silicone polymer (a3) of formula (S-VIII)

in which R represents —OH, —O—CH₃ or a —CH₃ group and m, n1 and n2 arenumbers whose sum (m+n1+n2) is between 1 and 2000, preferably between 50and 150, the sum (n1+n2) preferably assuming values from 0 to 1999 andfrom 49 to 149 and m preferably assuming values from 1 to 2000, from 1to 10.

According to the INCI declaration, these amino-modified oramino-functionalized silicone polymers are known as amodimethicones.

Regardless of which amino-modified silicones are used, agents (a)comprising an amino-modified silicone polymer whose amine number isabove 0.25 meq/g, preferably above 0.3 meq/g and above 0.4 meq/g, arepreferred. The amine number represents the milliequivalents of amine pergram of the amino-functional silicone. The amine number represents themilliequivalents of amine per gram of the amino-functional silicone.

In another preferred embodiment, an agent (a) is applied to thekeratinous material, wherein the agent (a) comprises at least oneamino-modified silicone polymer (a3) of the formula of formula (S-IX),

where

-   -   m and n mean numbers chosen so that the sum (n+m) is in the        range 1 to 1000,    -   n is a number in the range 0 to 999 and m is a number in the        range 1 to 1000,    -   R1, R2 and R3, which are the same or different, denote a hydroxy        group or a C1-4 alkoxy group,    -   wherein at least one of R1 to R3 represents a hydroxy group;

Other preferred methods include applying an agent (a) to the keratinousmaterial, said agent (a) comprising at least amino-functional siliconepolymer of the formula of the formula (S-X)

in which

-   -   p and q mean numbers chosen so that the sum (p+q) is in the        range 1 to 1000,    -   p is a number in the range 0 to 999 and q is a number in the        range 1 to 1000,    -   R1 and R2, which are different, denote a hydroxy group or a C1-4        alkoxy group, at least one of R1 to R2 denoting a hydroxy group.

The silicones of the formulas (S-IX) and (S-X) differ in the grouping atthe Si atom carrying the nitrogen-comprising group: In formula (S-IX),R2 represents a hydroxy group or a C1-4 alkoxy group, while the residuein formula (S-X) is a methyl group. The individual Si groupings, whichare marked with the indices m and n or p and q, do not have to bepresent as blocks; rather, the individual units can also be present in astatistically distributed manner, i.e., in the formulas (S-IX) and(S-X), not every R1-Si(CH₃)₂ group is necessarily bound to an—[O—Si(CH₃)₂] grouping.

Processes in which an agent (a) comprising at least one amino-modifiedsilicone polymer (a3) of the formula of the formula (S-XI) is applied tothe keratin fibers have also proved to be particularly effectiveregarding the desired effects

located in theA represents a group —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,b, n and c stand for integers between 0 and 1000,with the specifications

-   -   n>0 and b+c>0    -   at least one of the conditions A=—OH or D=—H is fulfilled.

In the above formula (S-XI), the individual siloxane units arestatistically distributed with the indices b, c and n, i.e., they do notnecessarily have to be block copolymers.

Particularly beneficial effects regarding the improvement of rubfastness were observed when an agent (a) comprising a special4-morpholinomethyl-substituted silicone polymer (a3) was applied to thekeratinous material in the procedures. This very particularly preferredamino-functionalized silicone polymer comprises at least one structuralunit of the formula (S-XIII)

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, wherein the agent comprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of the formula (S-XIII)

Particularly beneficial effects in terms of improving rub fastness werealso observed when an agent (a) comprising a special4-morpholinomethyl-substituted silicone polymer (a3) was applied to thekeratinous material in the procedures. This very particularly preferredamino-functionalized silicone polymer comprises structural units of theformulae (S-XII) and of the formula (S-XIII)

In an explicitly quite particularly preferred embodiment, the agent (a)comprises at least one amino-modified silicone polymer (a3) comprisingstructural units of the formula (S-XII) and of the formula (S-XIII)

Corresponding 4-morpholinomethyl-substituted silicone polymers aredescribed below.

A very particularly preferred amino-functionalized silicone polymer isknown as amodimethicone/morpholinomethyl silsesquioxane copolymer and iscommercially available in the form of the raw material Belsil ADM 8301 Efrom Wacker.

As a 4-morpholinomethyl-substituted silicone, for example, a siliconecan be used which has structural units of the formulae (S-XII),(S-XIII′) and (S-XIV′)

in whichR1 is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R2 is —CH₃, —OH, or —OCH₃.Particularly preferred agents (a) comprise at least one4-morpholinomethyl-substituted silicone of the formula (S-XV)

located in theR1 is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R2 is —CH₃, —OH, or —OCH₃.B represents a group —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,a, b and c stand independently for integers between 0 and 1000, with thecondition a+b+c>0m and n independently of each other stand for integers between 1 and1000

-   -   with the proviso that        -   at least one of the conditions B=—OH or D=—H is fulfilled,        -   the units a, b, c, m and n are distributed statistically or            blockwise in the molecule.

Structural formula (Si-VI) is intended to illustrate that the siloxanegroups n and m do not necessarily have to be directly bonded to aterminal grouping B or D, respectively. Rather, in preferred formulas(Si-VI) a>0 or b>0 and in particularly preferred formulas (Si-VI) a>0and c>0, i.e., the terminal grouping B or D is preferably attached to adimethylsiloxy grouping. Also, in formula (Si-VI), the siloxane units a,b, c, m and n are preferably statistically distributed.

The silicones used as contemplated herein represented by formula (Si-VI)can be trimethylsilyl-terminated (D or B=—Si(CH₃)₃), but they can alsobe dimethylsilylhydroxy-terminated on two sides ordimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated onone side. Silicones particularly preferred in the context of the presentdisclosure are selected from silicones in which

B = —O—Si(CH₃)₂OH and D = —Si(CH₃)₃ B = —O—Si(CH₃)₂OH and D =—Si(CH₃)₂OH B = —O—Si(CH₃)₂OH and D = —Si(CH₃)₂OCH₃ B = —O—Si(CH₃)₃ andD = —Si(CH₃)₂OH B = —O—Si(CH₃)₂OCH₃ and D = —Si(CH₃)₂OHto everyone.

To produce particularly resistant films, the agent (a) comprises thesilicone polymer(s), in particular the alkoxy-modified and/or theamino-modified silicone polymers, preferably in specific ranges ofamounts.

Particularly flexible films of low tack were obtained when an agent (a)was used in the process which comprises—based on the total weight of theagent (a)—one or more silicone polymers (a3) in a total amount of from0.1 to 8% by weight, preferably from 0.1 to 5% by weight, morepreferably from 0.1 to 3% by weight and very particularly preferablyfrom 0.1 to 0.5% by weight.

In the context of a further preferred embodiment, the agent (a)comprises—based on the total weight of the agent (a)—one or moresilicone polymers (a3) in a total amount of from 0.1 to 15% by weight,preferably from 0.5 to 12% by weight, more preferably from 1 to 10% byweight and very particularly preferably from 2 to 8% by weight.

In an explicitly quite particularly preferred embodiment, the agent (a)comprises —based on the total weight of the agent (a)—one or morealkoxy-modified silicone polymers (a3) in a total amount of from 0.1 to15% by weight, preferably from 0.5 to 12% by weight, more preferablyfrom 1 to 10% by weight and very particularly preferably from 2 to 8% byweight.

In the context of an explicitly quite particularly preferred embodiment,the agent (a) comprises—based on the total weight of the agent (a)—oneor more amino-modified silicone polymers in a total amount of from 0.1to 15% by weight, preferably from 0.5 to 12% by weight, more preferablyfrom 1 to 10% by weight and very particularly preferably from 2 to 8% byweight.

pH Value of the Agent (a)

It has been found preferable if the agent (a) is made up in the form ofa water-comprising agent adjusted to an alkaline pH.

To adjust the pH value, the agent (a) may contain at least onealkalizing agent.

To adjust the desired pH, the agents (a) may therefore also contain atleast one alkalizing agent. The pH values for the purposes of thepresent disclosure are pH values measured at a temperature of 22° C.

As alkalizing agent, agent (a) may contain, for example, ammonia,alkanolamines and/or basic amino acids.

The alkanolamines that can the agent in the compositions are preferablyselected from primary amines having a C₂-C₆ alkyl parent carrying atleast one hydroxyl group. Preferred alkanolamines are selected from thegroup formed by 2-aminoethan-1-ol (monoethanolamine),3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol,2-amino-2-methylpropan-1,3-diol.

Particularly preferred alkanolamines are selected from 2-aminoethan-1-oland/or 2-amino-2-methylpropan-1-ol. in a particularly preferredembodiment the agent comprises, as alkalizing agent, an alkanolamineselected from 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol.

For the purposes of the present disclosure, an amino acid is an organiccompound comprising in its structure at least one protonatable aminogroup and at least one —COOH or one —SO₃H group. Preferred amino acidsare aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acidsand o-aminocarboxylic acids, whereby α-aminocarboxylic acids areparticularly preferred.

Basic amino acids are those amino acids which have an isoelectric pointpI greater than 7.

Basic α-aminocarboxylic acids contain at least one asymmetric carbonatom. In the context of the present disclosure, both enantiomers can beused equally as specific compounds or their mixtures, especially asracemates. However, it is particularly advantageous to use the naturallypreferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine and histidine, especially preferablyarginine and lysine. In a further particularly preferred embodiment, thealkalizing agent is a basic amino acid selected from the group ofarginine, lysine, ornithine and/or histidine.

In addition, the product may contain other alkalizing agents, especiallyinorganic alkalizing agents. Inorganic alkalizing agents usable ascontemplated herein are preferably selected from the group formed bysodium hydroxide, potassium hydroxide, calcium hydroxide, bariumhydroxide, sodium phosphate, potassium phosphate, sodium silicate,sodium metasilicate, potassium silicate, sodium carbonate and potassiumcarbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine,lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide,calcium hydroxide, barium hydroxide, sodium phosphate, potassiumphosphate, sodium silicate, sodium metasilicate, potassium silicate,sodium carbonate and potassium carbonate.

Although the agents (a) are preferably adjusted to pH values in thealkaline range, it may nevertheless be necessary in principle to alsouse acidifiers in small quantities for fine adjustment of the desired pHvalue. Acidifiers suitable as contemplated herein are, for example,citric acid, lactic acid, acetic acid or also dilute mineral acids (suchas hydrochloric acid, sulfuric acid, phosphoric acid).

However, in the course of the work leading to the present disclosure, ithas been found that the presence of the alkalizing agent or theadjustment of the alkaline pH is essential for the formation ofresistant films on the keratinous material. The presence of excessiveamounts of acids can have a negative effect on the strength of thefilms. For this reason, it has proved preferable to keep the quantitiesof acids used in the agent (a) as low as possible. For this reason, itis advantageous if the total amount of organic and/or inorganic acidsincluded in the agent (a) does not exceed a certain value.

In a further preferred embodiment, the total amount of organic acidsfrom the group comprising citric acid, tartaric acid, malic acid andlactic acid included in the agent (a) is below 1% by weight, preferablybelow 0.7% by weight, more preferably below 0.5% by weight, even morepreferably below 0.1% by weight and most preferably below 0.01% byweight.

In a further preferred embodiment, the total amount of inorganic acidsfrom the group comprising hydrochloric acid, sulfuric acid andphosphoric acid included in the agent (a) is below 1% by weight,preferably below 0.7% by weight, more preferably below 0.5% by weight,still more preferably below 0.1% by weight and very particularlypreferably below 0.01% by weight.

The maximum total amounts of the acids included in the agent (a) givenabove are always based on the total weight of the agent (a).

Agent (b)

The method of treatment of keratinous material includes, in addition tothe application of agent (a), the application of agent (b). The agent(b) used in the process comprises at least one sealing reagent (b1).

The agent (b) is a post-treatment agent and the application of agent (b)to the keratinous material treated with agent (a) has the effect ofmaking the colorations obtained in the process more durable. Inparticular, the use of agent (b) can improve the fastness to washing andthe fastness to rubbing of the dyeing's obtained in the process.

It is preferred that the sealing reagent (b1) comprises a compoundselected from the group of film-forming polymers, alkalizing agents,acidifying agents, and mixtures thereof.

It may be preferred that the sealing reagent (b1) comprises afilm-forming polymer.

Polymers are macromolecules with a molecular weight of at least 1000g/mol, preferably of at least 2500 g/mol, particularly preferably of atleast 5000 g/mol, which include identical, repeating organic units. Thepolymers of the present disclosure may be synthetically producedpolymers which are manufactured by polymerization of one type of monomeror by polymerization of diverse types of monomer which are structurallydifferent from each other. If the polymer is produced by polymerizing atype of monomer, it is called a homo-polymer. If structurally differentmonomer types are used in polymerization, the resulting polymer iscalled a copolymer.

The maximum molecular weight of the polymer depends on the degree ofpolymerization (number of polymerized monomers) and the batch size andis determined by the polymerization method. In terms of the presentdisclosure, it is preferred if the maximum molecular weight of thefilm-forming hydrophobic polymer is not more than 107 g/mol, preferablynot more than 106 g/mol, and particularly preferably not more than 10g/mol.

As contemplated herein, a film-forming polymer is a polymer which canform a film on a substrate, for example on a keratinic material or akeratinic fiber. The formation of a film can be demonstrated, forexample, by viewing the polymer-treated keratinous material under amicroscope.

The film-forming polymers in agent (b) can be hydrophilic orhydrophobic.

In a first embodiment, it may be preferred to use at least onehydrophobic film-forming polymer as sealing reagent (b1) in agent (b).

A hydrophobic polymer is a polymer that has a solubility in water at 25°C. (760 mmHg) of less than 1% by weight.

The water solubility of the film-forming, hydrophobic polymer can bedetermined in the following way, for example. 1 g of the polymer isplaced in a beaker. Make up to 100 g with water. A stir-fish is added,and the mixture is heated to 25° C. on a magnetic stirrer whilestirring. It is stirred for 60 minutes. The aqueous mixture is thenvisually assessed. If the polymer-water mixture cannot be assessedvisually due to a high turbidity of the mixture, the mixture isfiltered. If a proportion of undissolved polymer remains on the filterpaper, the solubility of the polymer is less than 1% by weight.

These include acrylic acid-type polymers, polyurethanes, polyesters,polyamides, polyureas, cellulose polymers, nitrocellulose polymers,silicone polymers, acrylamide-type polymers and polyisoprenes.

Particularly well suited film-forming, hydrophobic polymers are, forexample, polymers from the group of copolymers of acrylic acid,copolymers of methacrylic acid, homopolymers or copolymers of acrylicacid esters, homopolymers or copolymers of methacrylic acid esters,homopolymers or copolymers of acrylic acid amides, homopolymers orcopolymers of methacrylic acid amides, copolymers of vinylpyrrolidone,copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymersor copolymers of ethylene, homopolymers or copolymers of propylene,homopolymers or copolymers of styrene, polyurethanes, polyesters and/orpolyamides.

In a further preferred embodiment, the agent (b) comprises at least onefilm-forming, hydrophobic polymer as sealing reagent (b1), which isselected from the group of the copolymers of acrylic acid, thecopolymers of methacrylic acid, the homopolymers or copolymers ofacrylic acid esters, the homopolymers or copolymers of methacrylic acidesters homopolymers or copolymers of acrylic acid amides, homopolymersor copolymers of methacrylic acid amides, copolymers ofvinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinylacetate, homopolymers or copolymers of ethylene, homopolymers orcopolymers of propylene, homopolymers or copolymers of styrene,polyurethanes, polyesters and/or polyamides.

The film-forming hydrophobic polymers, which are selected from the groupof synthetic polymers, polymers obtainable by radical polymerization ornatural polymers, have proved to be particularly suitable for solvingthe problem as contemplated herein.

Other particularly well-suited film-forming hydrophobic polymers can beselected from the homopolymers or copolymers of olefins, such ascycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinylamides, the esters or amides of (meth)acrylic acid having at least oneC₁-C₂₀ alkyl group, an aryl group or a C₂-C₁₀ hydroxyalkyl group.

Other film-forming hydrophobic polymers may be selected from the homo-or copolymers of isooctyl (meth)acrylate, isononyl (meth)acrylate,2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate), isopentyl(meth)acrylate, n-butyl (meth)acrylate), isobutyl (meth)acrylate, ethyl(meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate,stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl (meth)acrylate and/or mixtures thereof.

Further film-forming hydrophobic polymers can be selected from the homo-or copolymers of (meth)acrylamide, N-alkyl(meth)acrylamides, those withC2-C18 alkyl groups, such as N-ethyl acrylamide, N-tert-butylacrylamide,le N-octylacrylamide, N-di(C1-C4)alkyl(meth)acrylamide.

Other preferred anionic copolymers are, for example, copolymers ofacrylic acid, methacrylic acid or their C₁-C₆ alkyl esters, as they aremarketed under the INCI Declaration Acrylates Copolymers. A suitablecommercial product is for example Aculyn® 33 from Rohm & Haas.Copolymers of acrylic acid, methacrylic acid or their C₁-C₆ alkyl estersand the esters of an ethylenically unsaturated acid and an alkoxylatedfatty alcohol are also preferred. Suitable ethylenically unsaturatedacids are especially acrylic acid, methacrylic acid and itaconic acid;suitable alkoxylated fatty alcohols are especially steareth-20 orceteth-20.

Very particularly preferred polymers on the market are, for example,Aculyn® 22 (Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 28(Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 2001@(Acrylates/Steareth-20 Itaconate Copolymer), Structure 3001@(Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus®(Acrylates/Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer),Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C10-30 AlkylAcrylate Crosspolymer), Synthalen W 2000® (Acrylates/Palmeth-25 AcrylateCopolymer) or the Rohme und Haas distributed Soltex OPT(Acrylates/C12-22 Alkyl methacrylate Copolymer).

Suitable polymers based on vinyl monomers may include, for example, thehomopolymers and copolymers of N-vinylpyrrolidone, vinylcaprolactam,vinyl-(C1-C6)alkyl-pyrrole, vinyl oxazole, vinyl thiazole, vinylpyrimidine or vinyl imidazole.

Also particularly suitable are the copolymersoctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, suchas those sold commercially by NATIONAL STARCH under the trade namesAMPHOMER® or LOVOCRYL® 47, or the copolymers ofacrylates/octylacrylamides sold under the trade names DERMACRYL® LT andDERMACRYL® 79 by NATIONAL STARCH.

Suitable olefin-based polymers include homopolymers and copolymers ofethylene, propylene, butene, isoprene and butadiene.

In another embodiment, the film-forming hydrophobic polymers may be theblock copolymers comprising at least one block of styrene or thederivatives of styrene. These block copolymers may be copolymerscomprising one or more blocks in addition to a styrene block, such asstyrene/ethylene, styrene/ethylene/butylene, styrene/butylene,styrene/isoprene, styrene/butadiene. Such polymers are commerciallydistributed by BASF under the trade name “Luvitol HSB”.

Surprisingly, it was found that particularly intense and washfastcolorations could be obtained when agent (b) included at least onefilm-forming polymer as sealing reagent (b1), which was selected fromthe group of homopolymers and copolymers of acrylic acid, homopolymersand copolymers of methacrylic acid, homopolymers and copolymers ofacrylic acid esters, homopolymers and copolymers of methacrylic acidesters, homopolymers and copolymers of acrylic acid amides, homopolymersand copolymers of methacrylic acid amides, homopolymers and copolymersof vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol,homopolymers and copolymers of vinyl acetate, homopolymers andcopolymers of ethylene, homopolymers and copolymers of propylene,homopolymers and copolymers of styrene, polyurethanes, polyesters andpolyamides.

In a further preferred embodiment, the agent (b) comprises at least onefilm-forming polymer as sealing agent (b1), which is selected from thegroup of the homopolymers and copolymers of acrylic acid, thehomopolymers and copolymers of methacrylic acid, the homopolymers andcopolymers of acrylic acid esters, the homopolymers and copolymers ofmethacrylic acid esters, homopolymers and copolymers of acrylic acidamides, homopolymers and copolymers of methacrylic acid amides,homopolymers and copolymers of vinylpyrrolidone, homopolymers andcopolymers of vinyl alcohol, homopolymers and copolymers of vinylacetate, homopolymers and copolymers of ethylene, homopolymers andcopolymers of propylene, homopolymers and copolymers of styrene,polyurethanes, polyesters and polyamides.

In a further embodiment, it may be preferred to use at least onehydrophilic film-forming polymer as sealing reagent (b1) in agent (b).

A hydrophilic polymer is a polymer that has a solubility in water at 25°C. (760 mmHg) of more than 1% by weight, preferably more than 2% byweight.

The water solubility of the film-forming, hydrophilic polymer can bedetermined in the following way, for example. 1 g of the polymer isplaced in a beaker. Make up to 100 g with water. A stir-fish is added,and the mixture is heated to 25° C. on a magnetic stirrer whilestirring. It is stirred for 60 minutes. The aqueous mixture is thenvisually assessed. A completely dissolved polymer appearsmacroscopically homogeneous. If the polymer-water mixture cannot beassessed visually due to a high turbidity of the mixture, the mixture isfiltered. If no undissolved polymer remains on the filter paper, thesolubility of the polymer is more than 1% by weight.

Nonionic, anionic and cationic polymers can be used as film-forming,hydrophilic polymers.

Suitable film-forming hydrophilic polymers may be selected, for example,from the group comprising polyvinylpyrrolidone (co)polymers, polyvinylalcohol (co)polymers, vinyl acetate (co)polymers, the carboxyvinyl(co)polymers, the acrylic acid (co)polymers, the methacrylic acid(co)polymers, the natural gums, the polysaccharides and/or theacrylamide (co)polymers.

Furthermore, it is particularly preferred to use polyvinylpyrrolidone(PVP) and/or a vinylpyrrolidone-comprising copolymer as film-forminghydrophilic polymer.

In another very particularly preferred embodiment, the agent (b)comprises at least one film-forming, hydrophilic polymer as sealingreagent (b1), which is selected from the group of polyvinylpyrrolidone(PVP) and the copolymers of polyvinylpyrrolidone.

It is further preferred if the agent comprises polyvinylpyrrolidone(PVP) as the film-forming hydrophilic polymer. Surprisingly, the washfastness of the stains obtained with PVP-comprising agents (b) was alsoparticularly good.

Particularly well-suited polyvinylpyrrolidones are available, forexample, under the name Luviskol® K from BASF SE, especially Luviskol® K90 or Luviskol® K 85 from BASF SE.

The polymer PVP K30, which is marketed by Ashland (ISP, POI Chemical),can also be used as another explicitly very well suitedpolyvinylpyrrolidone (PVP). PVP K 30 is a polyvinylpyrrolidone which ishighly soluble in cold water and has the CAS number 9003-39-8. Themolecular weight of PVP K 30 is about 40000 g/mol.

Other particularly suitable polyvinylpyrrolidones are the substancesknown under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60,LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and availablefrom BASF.

The use of film-forming hydrophilic polymers as sealing reagent (b1)from the group of copolymers of polyvinylpyrrolidone also led toparticularly good and washfast color results.

Vinylpyrrolidone-vinyl ester copolymers, such as those marketed underthe trademark Luviskol® (BASF), are particularly suitable film-forminghydrophilic polymers. Luviskol® VA 64 and Luviskol® VA 73, bothvinylpyrrolidone/vinyl acetate copolymers, are particularly preferrednon-ionic polymers.

Of the vinylpyrrolidone-comprising copolymers, a styrene/VP copolymerand/or a vinylpyrrolidone-vinyl acetate copolymer and/or a VP/DMAPAacrylates copolymer and/or a VP/vinyl caprolactam/DMAPA acrylatescopolymer are particularly preferred in cosmetic compositions.

Vinylpyrrolidone-vinyl acetate copolymers are marketed under the nameLuviskol® VA by BASF SE. For example, a VP/Vinyl Caprolactam/DMAPAAcrylates copolymer is sold under the trade name Aquaflex® SF-40 byAshland Inc. For example, a VP/DMAPA acrylates copolymer is marketed byAshland under the name Styleze CC-10 and is a highly preferredvinylpyrrolidone-comprising copolymer.

Other suitable copolymers of polyvinylpyrrolidone may also be thoseobtained by reacting N-vinylpyrrolidone with at least one furthermonomer from the group comprising V-vinylformamide, vinyl acetate,ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactoneand/or vinyl alcohol.

In another very particularly preferred embodiment, the agent (b)comprises at least one film-forming, hydrophilic polymer as sealingreagent (b1), which is selected from the group of polyvinylpyrrolidone(PVP), vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylenecopolymers, vinylpyrrolidone/propylene copolymers,vinylpyrrolidone/vinylcaprolactam copolymers,vinylpyrrolidone/vinylformamide copolymers and/or vinylpyrrolidone/vinylalcohol copolymers.

Another fussy copolymer of vinylpyrrolidone is the polymer known underthe INCI designation maltodextrin/VP copolymer.

Furthermore, intensively colored keratinous material, especially hair,could be obtained with particularly good wash fastness properties when anonionic film-forming hydrophilic polymer was used as the film-forminghydrophilic polymer.

In another embodiment, the agent (b) may comprise at least one nonionic,film-forming, hydrophilic polymer as sealing reagent (b1).

As contemplated herein, a non-ionic polymer is understood to be apolymer which in a protic solvent—such as water—under standardconditions does not carry structural units with permanent cationic oranionic groups, which must be compensated by counterions whilemaintaining electron neutrality. Cationic groups include quaternizedammonium groups but not protonated amines. Anionic groups includecarboxylic and sulphonic acid groups.

Preference is given to products comprising, as a non-ionic,film-forming, hydrophilic polymer, at least one polymer selected fromthe group of

-   -   Polyvinylpyrrolidone,    -   Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic        acids comprising 2 to 18 carbon atoms of N-vinylpyrrolidone and        vinyl acetate,    -   Copolymers of N-vinylpyrrolidone and N-vinylimidazole and        methacrylamide,    -   Copolymers of N-vinylpyrrolidone and N-vinylimidazole and        acrylamide,    -   Copolymers of N-vinylpyrrolidone with N,N-di(C1 to        C4)alkylamino-(C2 to C4)alkyl acrylamide.

If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it isagain preferable if the molar ratio of the structural units included inthe monomer N-vinylpyrrolidone to the structural units of the polymerincluded in the monomer vinyl acetate is in the range from 20:80 to80:20, in particular from 30:70 to 60:40. Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example, under thetrademarks Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 andLuviskol® VA 73 from BASF SE.

Another particularly preferred polymer is selected from the INCIdesignation VP/Methacrylamide/Vinyl Imidazole Copolymer, which isavailable under the trade name Luviset Clear from BASF SE.

Another particularly preferred nonionic, film-forming, hydrophilicpolymer is a copolymer of N-vinylpyrrolidone andN,N-dimethylaminopropylmethacrylamide, which is sold, for example, byISP under the INCI designation VP/DMAPA Acrylates Copolymer, e.g., underthe trade name Styleze® CC 10.

A cationic polymer is the copolymer of N-vinylpyrrolidone,N-vinylcaprolactam, N-(3-dimethylaminopropyl)methacrylamide and3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCIdesignation: Polyquaternium-69), which is marketed, for example, underthe trade name AquaStyle® 300 (28-32 wt. % active substance inethanol-water mixture, molecular weight 350000) by ISP.

Other suitable film-forming, hydrophilic polymers include

-   -   Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as        offered under the designations Luviquat® FC 370, FC 550 and the        INCI designation Polyquaternium-16 as well as FC 905 and HM 552,    -   Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, as they        are commercially available with acrylic acid esters and acrylic        acid amides as a third monomer component, for example under the        name Aquaflex® SF 40.

Polyquaternium-11 is the reaction product of diethyl sulphate with acopolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate.Suitable commercial products are available under the names Dehyquart® CC11 and Luviquat® PQ 11 PN from BASF SE or Gafquat 440, Gafquat 734,Gafquat 755 or Gafquat 755N from Ashland Inc.

Polyquaternium-46 is the reaction product of vinylcaprolactam andvinylpyrrolidone with methylvinylimidazolium methosulfate and isavailable for example under the name Luviquat® Hold from BASF SE.Polyquaternium-46 is preferably used in an amount of 1 to 5% byweight—based on the total weight of the cosmetic composition. Itparticularly prefers to use polyquaternium-46 in combination with acationic guar compound. It is even highly preferred thatpolyquaternium-46 is used in combination with a cationic guar compoundand polyquaternium-11.

Suitable anionic film-forming, hydrophilic polymers can be, for example,acrylic acid polymers, which can be in non-crosslinked or crosslinkedform. Such products are sold commercially under the trade names Carbopol980, 981, 954, 2984 and 5984 by Lubrizol or under the names Synthalen Mand Synthalen K by 3V Sigma (The Sun Chemicals, Inter Harz).

Examples of suitable film-forming, hydrophilic polymers from the groupof natural gums are xanthan gum, gellan gum, carob gum.

Examples of suitable film-forming hydrophilic polymers from the group ofpolysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose,ethyl cellulose and carboxymethyl cellulose.

Suitable film-forming, hydrophilic polymers from the group ofacrylamides are, for example, polymers prepared from monomers of(meth)acrylamido-C1-C4-alkyl sulfonic acid or salts thereof.Corresponding polymers may be selected from the polymers ofpolyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid,polyacrylamidopropanesulfonic acid,poly2-acrylamido-2-methylpropanesulfonic acid,poly-2-methylacrylamido-2-methylpropanesulfonic acid and/orpoly-2-methylacrylamido-n-butanesulfonic acid.

Preferred polymers of poly(meth)arylamido-C1-C4-alkyl-sulfonic acids arecrosslinked and at least 90% neutralized. These polymers can becrosslinked or non-crosslinked.

Cross-linked and fully or partially neutralized polymers of thepoly-2-acrylamido-2-methylpropane sulfonic acid type are available underthe INCI names “Ammonium Polyacrylamido-2-methyl-propanesulphonates” or“Ammonium Poly acryldimethyltauramides”.

Another preferred polymer of this type is the crosslinkedpoly-2-acrylamido-2methyl-propanesulfonic acid polymer sold by Clariantunder the trade name Hostacerin AMPS, which is partially neutralizedwith ammonia.

In another explicitly very particularly preferred embodiment, the agent(b) comprises at least one anionic, film-forming, polymer as sealingreagent (b1).

In this context, the best results were obtained when the agent (b)comprises, as sealing reagent (b1), at least one film-forming polymercomprising at least one structural unit of formula (P-I) and at leastone structural unit of formula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.

In a further preferred embodiment, the agent (b) comprises at least onefilm-forming polymer as sealing reagent (b1), which comprises at leastone structural unit of the formula (P-I) and at least one structuralunit of the formula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.When M represents a hydrogen atom, the structural unit of the formula(P-I) is based on an acrylic acid unit.When M stands for an ammonium counterion, the structural unit of theformula (P-I) is based on the ammonium salt of acrylic acid.When M stands for a sodium counterion, the structural unit of theformula (P-I) is based on the sodium salt of acrylic acid.When M stands for a potassium counterion, the structural unit of theformula (P-I) is based on the potassium salt of acrylic acid.If M stands for a half equivalent of a magnesium counterion, thestructural unit of the formula (P-I) is based on the magnesium salt ofacrylic acid.If M stands for a half equivalent of a calcium counterion, thestructural unit of the formula (P-I) is based on the calcium salt ofacrylic acid.

The film-forming polymer or polymers are preferably used in specificranges of amounts in the agent (b). In this context, it has provedparticularly preferable for solving the problem as contemplated hereinif the agent (b) comprises—based on the total weight of the agent(b)—one or more film-forming polymers as sealing reagent (b1) in a totalamount of from 0.1 to 18% by weight, preferably from 1 to 16% by weight,more preferably from 5 to 14.5% by weight and very particularlypreferably from 8 to 12% by weight.

In a further preferred embodiment, the agent (b) comprises—based on thetotal weight of the agent (b)—one or more film-forming polymers assealing reagent (b1) in a total amount of from 0.1 to 18% by weight,preferably from 1 to 16% by weight, more preferably from 5 to 14.5% byweight and very particularly preferably from 8 to 12% by weight.

The application of agent (b) comprising a film-forming polymer assealing reagent (b1) is intended to seal and/or fix the colored filminitially produced by the application of agent (a). With application ofthe second agent (b) with a film-forming polymer as sealing reagent(b1), the film-forming polymer (b1) is deposited on the colored filmproduced in the first layer in the form of a further film. Themultilayer film system created in this way exhibits improved resistanceto external influences.

Here, the film produced by the agent (b) comprising a film-formingpolymer as sealing reagent (b1) is preferably not colored itself. Inthis way, it can also be ensured that any abrasion to a certain extentof the second film formed by agent (b) does not lead to any colorchanges in the entire film system. It is therefore particularlypreferred if the agent (b) comprises no or only exceedingly lesseramounts of colorant compounds.

In an alternative embodiment, the sealing reagent (b1) comprises analkalizing agent.

Particularly preferably, the alkalizing agent is selected from the groupof ammonia, C₂-C₆ alkanolamines, basic amino acids, alkali metalhydroxides and alkaline earth metal hydroxides.

In another particularly preferred embodiment, the agent (b) comprises atleast one alkalizing agent as sealing reagent (b1), which is selectedfrom the group of ammonia, C₂-C₆ alkanolamines, basic amino acids,alkali metal hydroxides, alkaline earth metal hydroxides, alkali metalsilicates, alkali metal metasilicates, alkaline earth metal silicates,alkaline earth metal metasilicates, alkali metal carbonates and alkalineearth metal carbonates.

It has been found that aftertreatment with an agent (b) comprisingammonia exerts a particularly good influence on improving the washfastness and rub fastness of the dyeing's obtained in the process.

In the context of a further very particularly preferred embodiment, theagent (b) comprises ammonia as sealing reagent (b1).

Satisfactory results were also obtained when agent (b) included at leastone C₂-C₆ alkanolamine as sealing reagent (b1).

The alkanolamines that can be used in agent (b) can be selected, forexample, from the group of primary amines having a C₂-C₆ alkyl parentcarrying at least one hydroxyl group. Preferred alkanolamines areselected from the group formed by 2-aminoethan-1-ol (monoethanolamine),3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol,2-amino-2-methylpropan-1,3-diol.

In a further preferred embodiment, the agent (b) comprises, as sealingreagent (b1), at least one alkalizing agent from the group ofalkanolamines, which is preferably selected from the group of2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol,4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol,1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol,1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol and2-amino-2-methylpropane-1,3-diol.

Likewise, satisfactory results were obtained when agent (b) included atleast one basic amino acid as sealing reagent (b1).

For the purposes of the present disclosure, an amino acid is an organiccompound comprising in its structure at least one protonatable aminogroup and at least one —COOH or one —SO₃H group. Preferred amino acidsare aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acidsand o-aminocarboxylic acids, whereby α-aminocarboxylic acids areparticularly preferred.

As contemplated herein, basic amino acids are those amino acids whichhave an isoelectric point pI of greater than 7.0.

Basic α-aminocarboxylic acids contain at least one asymmetric carbonatom. In the context of the present disclosure, both enantiomers can beused equally as specific compounds or their mixtures, especially asracemates. However, it is particularly advantageous to use the naturallypreferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine and histidine, especially preferablyarginine and lysine. In a further particularly preferred embodiment, thesealing reagent (b1) is an alkalizing agent comprising a basic aminoacid selected from the group of arginine, lysine, ornithine and/orhistidine.

In a further preferred embodiment, the agent (b) comprises as sealingreagent (b1) at least one alkalizing agent selected from the group ofbasic amino acids, which is preferably selected from the group ofarginine, lysine, ornithine and histidine.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal hydroxide as sealing reagent (b1). Examples ofwell-suited alkali metal hydroxides are sodium hydroxide and potassiumhydroxide.

Satisfactory results were also obtained when the agent (b) included, assealing reagent (b1), an alkalizing agent comprising at least onealkaline earth metal hydroxide. Suitable alkaline earth metal hydroxidesinclude magnesium hydroxide, calcium hydroxide and barium hydroxide.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal silicate and/or alkali metal metasilicate assealing reagent (b1). Suitable alkali metal silicates include sodiumsilicate and potassium silicate. Suitable alkali metal metasilicatesinclude sodium metasilicate and potassium metasilicate.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal carbonate and/or alkaline earth metal carbonateas sealing reagent (b1). Suitable alkali metal carbonates include sodiumcarbonate and potassium carbonate. Suitable alkaline earth metalcarbonates include magnesium carbonate and calcium carbonate.

Within the group of the sealing reagents (b1) in the form of analkalizing agent, ammonia, C₂-C₆ alkanolaminenes, basic amino acids andalkali metal hydroxides have proved to be particularly suitable.

In the context of a further particularly preferred embodiment, agent (b)comprises as sealing reagent (b1) at least one alkalizing agent selectedfrom the group of ammonia, C₂-C₆ alkanolamines, basic amino acids andalkali metal hydroxides.

In another particularly preferred embodiment, agent (b) comprises, assealing reagent (b1), at least one alkalizing agent selected from thegroup of ammonia, 2-aminoethan-1-ol, 3-aminopropan-1-ol,4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol,1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol,1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol,2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine,histidine, sodium hydroxide and potassium hydroxide.

Agent (b) comprises the alkalizing agent as a sealing reagent (b1) in acosmetic carrier, preferably in an aqueous cosmetic carrier.

In this context, it has been found preferable if the agent (b)comprises—based on the total weight of the agent (b)—5.0 to 99.0% byweight, preferably 15.0 to 97.0% by weight, more preferably 25.0 to97.0% by weight, still more preferably 35.0 to 97.0% by weight and veryparticularly preferably 45.0 to 97.0% by weight of water.

In the context of a further embodiment, agent (b) comprises—based on thetotal weight of the agent (b)—5.0 to 99.0% by weight, preferably 15.0 to97.0% by weight, more preferably 25.0 to 97.0% by weight, still morepreferably 35.0 to 97.0% by weight and very particularly preferably 45.0to 97.0% by weight of water.

The alkalizing agents included in the agent (b) exert an influence onthe pH value of the agent (b). It was found that certain alkaline pHvalues have a beneficial effect on the dyeing performance achievable inthe process and the fastness properties of the dyeing's.

For this reason, it is preferred that the agent (b) comprising analkalizing agent as sealing reagent (b1) has a pH of from 7.0 to 12.0,preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0, and mostpreferably from 8.5 to 9.5.

The pH value can be measured using the usual methods known from thestate of the art, such as pH measurement using glass electrodes viacombination electrodes or using pH indicator paper.

In another very particularly preferred embodiment, agent (b) comprisesan alkalizing agent as sealing reagent (b1) and has a pH of from 7.0 to12.0, preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0 andmost preferably from 8.5 to 9.5.

The pH values for the purposes of the present disclosure are pH valuesmeasured at a temperature of 22° C.

In a still further alternative embodiment, the sealing reagent (b1)comprises an acidifying agent.

Particularly preferably, the acidifying agent is selected from the groupof inorganic acids, organic acids and mixtures thereof.

Satisfactory results could be obtained when agent (b) comprises at leastone inorganic acid as sealing reagent (b1). Suitable inorganic acidsare, for example, phosphoric acid, sulfuric acid and/or hydrochloricacid, with sulfuric acid being particularly preferred.

In a further preferred embodiment, agent (b) comprises, as sealingreagent (b1), at least one acidifying agent selected from the group ofinorganic acids, which is preferably selected from the group ofphosphoric acid, sulfuric acid, hydrochloric acid and mixtures thereof.

In a further, even more preferred embodiment, the agent (b) comprisessulfuric acid as sealing reagent (b1).

Satisfactory results were also obtained when agent (b) included at leastone organic acid as sealing reagent (b1). The organic acid is preferablyselected from the group of formic acid, acetic acid, propionic acid,butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, glycericacid, Glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaicacid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid,elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid,mesaconic acid, camphoric acid, benzoic acid, o,m,p-phthalic acid,naphthoic acid, toluoylic acid, hydratropic acid, atropic acid, cinnamicacid, isonicotinic acid, nicotinic acid, bicarbamic acid,4,4′-dicyano-6,6′-binicotinic acid, 8-carbamoyloctanoic acid,1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid,1,2,4,6,7-napthalenepentaacetic acid, malonaldehyde acid,4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid orpropane tricarboxylic acid, glycolic acid, gluconic acid, lactic acid,maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid andmixtures thereof.

In a further preferred embodiment, the agent (b) comprises as sealingreagent (b1) at least one acidifying agent selected from the group oforganic acids, wherein the organic acid is preferably selected from thegroup of formic acid, acetic acid, propionic acid, butyric acid,isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalicacid, malonic acid, succinic acid, glutaric acid, glyceric acid,glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaic acid,sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidicacid, Maleic acid, fumaric acid, muconic acid, citraconic acid,mesaconic acid, camphoric acid, benzoic acid, o,m,p-phthalic acid,naphthoic acid, toluoylic acid, hydratropasic acid, atropasic acid,cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid,4,4′-dicyano-6,6′-binicotinic acid, 8-carbamoyloctanoic acid,1,2,4-pentane tricarboxylic acid, 2-pyrrole carboxylic acid,1,2,4,6,7-napthalene pentaacetic acid, malonaldehyde acid,4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid orpropane tricarboxylic acid, glycolic acid, gluconic acid, lactic acid,maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid andmixtures thereof.

In a further, even more preferred embodiment, the agent (b) comprisesacetic acid as sealing reagent (b1).

Also, suitable acidifiers include methanesulfonic acid and/or1-hydroxyethane-1,1-diphosphonic acid.

Within the group of the above-mentioned sealing reagents (b1) in theform of an acidifying agent, sulfuric acid and/or acetic acid haveproved to be particularly suitable.

In the context of a further particularly preferred embodiment, agent (b)comprises as sealing reagent (b1) at least one acidifying agent selectedfrom the group of sulfuric acid, acetic acid and mixtures thereof.

The agent (b) comprises the acidifying agent as sealing reagent (b1) ina cosmetic carrier, preferably in an aqueous cosmetic carrier.

The acidifying agents included in the agent (b) exert an influence onthe pH of the agent (b). It was found that acidic pH values also have abeneficial effect on the dyeing performance achievable in the processand the fastness properties of the dyeing's.

For this reason, it is preferred that the agent (b) comprising anacidifying agent as sealing reagent (b1) has a pH of from 2.0 to 6.5,preferably from 3.0 to 6.0, more preferably from 4.0 to 6.0, and mostpreferably from 4.5 to 5.5.

The pH value can be measured using the usual methods known from thestate of the art, such as pH measurement using glass electrodes viacombination electrodes or using pH indicator paper.

In another very particularly preferred embodiment, agent (b) comprisesan acidifying agent as sealing reagent (b1) and has a pH of from 2.0 to6.5, preferably from 3.0 to 6.0, more preferably from 4.0 to 6.0, andmost preferably from 4.5 to 5.5.

The pH values for the purposes of the present disclosure are pH valuesmeasured at a temperature of 22° C.

The application of agent (b) is intended to seal and fix the filminitially produced by the application of agent (a).

Other Ingredients in Products (a) and (b)

The agents (a) and (b) described above may also contain one or moreoptional ingredients.

The products may also contain one or more surfactants. The termsurfactants refer to surface-active substances. A distinction is madebetween anionic surfactants comprising a hydrophobic residue and anegatively charged hydrophilic head group, amphoteric surfactants, whichcarry both a negative and a compensating positive charge, cationicsurfactants, which in addition to a hydrophobic residue have apositively charged hydrophilic group, and non-ionic surfactants, whichhave no charges but strong dipole moments and are strongly hydrated inaqueous solution.

Zwitterionic surfactants are those surface-active compounds which carryat least one quaternary ammonium group and at least one —COOO⁽⁻⁾ or —SO₃⁽⁻⁾ group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines such as theN-alkyl-N,N-dimethylammonium-glycinate, for example thecocoalkyl-dimethylammoniumglycinate,N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example,cocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is thefatty acid amide derivative known under the INCI name cocamidopropylbetaine.

Ampholytic surfactants are surface-active compounds which, in additionto a C₈-C₂₄ alkyl or acyl group in the molecule, contain at least onefree amino group and at least one —COOH or —SO₃H group and can forminternal salts. Examples of suitable ampholytic surfactants areN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids each with about 8 to 24 C atoms in the alkyl group. Typicalexamples of amphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, amino-propionates, aminoglycinate,imidazoliniumbetaines and sulfobetaines.

Particularly preferred ampholytic surfactants areN-cocosalkylaminopropionate, cocosacylaminoethylaminopropionate andC₁₂-C₁₈-acylsarcosine.

The agents may also additionally contain at least one non-ionicsurfactant. Suitable non-ionic surfactants are alkyl polyglycosides aswell as alkylene oxide addition products to fatty alcohols and fattyacids with 2 to 30 mol ethylene oxide per mol fatty alcohol or fattyacid. Preparations with suitable properties are also obtained if theycontain as non-ionic surfactants fatty acid esters of ethoxylatedglycerol reacted with at least 2 mol ethylene oxide.

In addition, the products may also contain at least one cationicsurfactant. Cationic surfactants are surfactants, i.e., surface-activecompounds, each with one or more positive charges. Cationic surfactantscontain only positive charges. Usually, these surfactants are composedof a hydrophobic part and a hydrophilic head group, the hydrophobic partusually comprising a hydrocarbon backbone (e.g., comprising one or twolinear or branched alkyl chains) and the positive charge(s) being in thehydrophilic head group. Examples of cationic surfactants are

-   -   quaternary ammonium compounds which may carry one or two alkyl        chains with a chain length of 8 to 28 carbon atoms as        hydrophobic radicals,    -   quaternary phosphonium salts substituted by one or more alkyl        chains having a chain length of 8 to 28 carbon atoms or    -   tertiary sulfonium salts.

Furthermore, the cationic charge can also be part of a heterocyclic ring(e.g., an imidazolium ring or a pyridinium ring) in the form of an oniumstructure. In addition to the functional unit carrying the cationiccharge, the cationic surfactant may also contain other unchargedfunctional groups, as is the case for example with esterquats. Thecationic surfactants are used in a total quantity of 0.1 to 45 wt. %,preferably 1 to 30 wt. % and most preferably 1 to 15 wt. %—based on thetotal weight of the respective agent.

Furthermore, the agents may also contain at least one anionicsurfactant. Anionic surfactants are surface-active agents withexclusively anionic charges (neutralized by a corresponding countercation). Examples of anionic surfactants are fatty acids, alkylsulphates, alkyl ether sulphates and ether carboxylic acids with 12 to20 C atoms in the alkyl group and up to 16 glycol ether groups in themolecule.

The anionic surfactants are used in a total quantity of 0.1 to 45 wt. %,preferably 1 to 30 wt. % and most preferably 1 to 15 wt. %—based on thetotal weight of the respective agent.

The agent (a) and/or agent (b) may further comprise a matting agent.Suitable matting agents include, for example, (modified) starches,waxes, talc and/or (modified) silicas. The amount of matting agent ispreferably between 0.1 and 10% by weight based on the total amount ofagent (a) or agent (b). Preferably, agent (a) comprises a matting agent.

The agents may also contain other active ingredients, auxiliaries andadditives, such as solvents; fatty ingredients such as C₈-C₃₀ fatty acidtriglycerides, C₈-C₃₀ fatty acid monoglycerides, C₈-C₃₀ fatty aciddiglycerides and/or the hydrocarbons; structurants such as glucose,maleic acid and lactic acid, hair-conditioning compounds such asphospholipids, for example lecithin and kephalins; perfume oils,dimethyl isosorbide and cyclodextrins; fiber structure-improving activeingredients, in particular mono-, di- and oligosaccharides such asglucose, galactose, fructose, fructose and lactose; dyes for coloringthe product; anti-dandruff active ingredients such as piroctone olamine,zinc omadine and climbazole; amino acids and oligopeptides; proteinhydrolysates on an animal and/or vegetable basis, as well as in the formof their fatty acid condensation products or optionally anionically orcationically modified derivatives; vegetable oils; light stabilizers andUV blockers; active ingredients such as panthenol, pantothenic acid,pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts,and bisabolol; Polyphenols, in particular hydroxycinnamic acids,6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins,leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;ceramides or pseudoceramides; vitamins, provitamins and vitaminprecursors; plant extracts; Fats and waxes such as fatty alcohols,beeswax, montan wax and kerosenes; swelling and penetrating agents suchas glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas and primary, secondary and tertiaryphosphates; opacifiers such as latex, styrene/PVP and styrene/acrylamidecopolymers; pearlescent agents such as ethylene glycol mono- anddistearate as well as PEG-3-distearate; and blowing agents such aspropane-butane mixtures, N₂O, dimethyl ether, CO₂ and air.

The selection of these other substances will be made by the specialistaccording to the desired properties of the agents. Regarding otheroptional components and the quantities of these components used,explicit reference is made to the relevant manuals known to thespecialist. The additional active ingredients and auxiliary substancesare preferably used in the preparations as contemplated herein inquantities of 0.0001 to 25 wt. % each, 0.0005 to 15 wt. %, based on thetotal weight of the respective agent.

Process for Dyeing Keratinous Materials

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous materials, to human hair. Thus, agents (a) and (b) arethe ready-to-use agents. The agents (a) and (b) are different.

In principle, agents (a) and (b) can be applied simultaneously orsuccessively, whereby successive application is preferred.

The best results were obtained when agent (a) was first applied to thekeratinous materials in a first step and agent (b) was applied in asecond step.

Quite particularly preferred, therefore, is a process for treatingkeratinous material, for coloring keratinous material, in particularhuman hair, comprising the following steps in the order indicated:

-   -   in a first step, applying an agent (a) to the keratinous        material, the agent comprising (a):        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and 3) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and    -   In a second step, applying an agent (b) to the keratinous        material, the agent comprising (b):        (b1) at least one sealing reagent.

Moreover, to impart a high leaching resistance to the dyed keratinousmaterial over a longer period, agents (a) and (b) are particularlypreferably applied within the same dyeing process, which means thatthere is a period of a maximum of several hours between the applicationof agents (a) and (c).

In a further preferred embodiment, agent (a) is applied first and agent(b) is applied thereafter, the period between the application of agents(a) and (b) being at most 24 hours, preferably at most 12 hours andparticularly preferably at most 6 hours.

A distinguishing feature of the agent (a) is its content of at least onereactive organic silicon compound (a1). The reactive organic siliconcompound(s) (a1) undergoes an oligomerization or polymerization reactionand thus functionalizes the hair surface as soon as it encounters it. Inthis way, a first, film is formed. The coloring compounds (a2) areincorporated into the film so that it is colored. In the second step ofthe process, a second agent (b) is now applied to the hair. During theapplication of the agent (b) comprising at least one film-formingpolymer as sealing reagent (b1), the latter interacts with the silanefilm and is thus bound to the keratinous materials. During theapplication of agent (b) comprising at least one alkalizing agent oracidifying agent as sealing reagent (b1), the formation of the silanefilm is positively influenced.

In the context of a further form of execution, a procedure comprisingthe following steps in the order indicated is particularly preferred

(1) Application of the agent (a) on the keratinous material,(2) Allow the agent (a) to act for a period of 10 seconds to 10 minutes,preferably from 10 seconds to 5 minutes,(3) if necessary, rinse the keratinous material with water,(4) Application of agent (b) on the keratinous material,(5) Allowing the agent (b) to act for a period of 30 seconds to 30minutes, preferably from 30 seconds to 10 minutes,(6) Rinse the keratinous material with water.

The rinsing of the keratinous material with water in steps (3) and (6)of the process is understood, as contemplated herein, to mean that onlywater is used for the rinsing process, without any other agents otherthan agents (a) and (b).

In step (1), agent (a) is first applied to the keratinous materials, inparticular human hair.

After application, the agent (a) is left to act on the keratinousmaterials. In this context, application times from 10 seconds to 10minutes, preferably from 20 seconds to 5 minutes and especiallypreferably from 30 seconds to 2 minutes on the hair have proven to beparticularly beneficial.

In a preferred embodiment of the process, the agent (a) can now berinsed from the keratinic materials before the agent (b) is applied tothe hair in the subsequent step.

Stains with equally good wash fastnesses were obtained when agent (b)was applied to the keratinous materials that were still exposed to agent(a).

In step (4), agent (b) is now applied to the keratinous materials. Afterapplication, let the agent (b) act on the hair.

Even with a short contact time of the agent (b), the process allows theproduction of dyeing's with particularly good intensity and washfastness. Application times from 10 seconds to 10 minutes, preferablyfrom 20 seconds to 5 minutes and most preferably from 30 seconds to 3minutes on the hair have proven to be particularly beneficial.

In step (6), the agent (b) (and any agent (a) still present) is nowrinsed out of the keratinous material with water.

In this embodiment, the sequence of steps (1) to (6) preferably takesplace within 24 hours.

Agent (a) comprises, with the organic silicon compound(s), a class ofhighly reactive compounds that can undergo hydrolysis or oligomerizationand/or polymerization when used. As a result of their high reactivity,these organic silicon compounds form a film on the keratinous material.

To avoid premature oligomerization or polymerization, it is ofconsiderable advantage to the user to prepare the ready-to-use agent (a)only shortly before application.

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms, and        the second agent (a″) comprises at least one colorant compound        (a2) comprising at least one effect pigment which comprises a) a        substrate platelet and β) a coating, the coating having at least        one layer which is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        comprising,        (2) Application of the agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of 10 seconds to 10        minutes, preferably from 10 seconds to 5 minutes,        (4) if necessary, rinse the keratinous material with water,        (5) Application of agent (b) on the keratinous material,        (6) Allowing the agent (b) to act for a period of 30 seconds to        30 minutes, preferably from 30 seconds to 10 minutes,        (7) Rinse the keratinous material with water.

To be able to provide a formulation that is as stable as possible instorage, the agent (a′) itself is preferably formulated to be low inwater or water-free.

In a preferred embodiment, the agent (a′)—based on the total weight ofthe agent (a′)—comprises a water content of from 0.001 to 10% by weight,preferably from 0.5 to 9% by weight, more preferably from 1 to 8% byweight and very particularly preferably from 1.5 to 7% by weight.

The agent (a″) comprises water. In a preferred embodiment, the agent(a″)—based on the total weight of the agent (a2)—has a water content offrom 15 to 100% by weight, preferably from 35 to 100% by weight, morepreferably from 55 to 100% by weight, still more preferably from 65 to100% by weight and very particularly preferably from 75 to 100% byweight.

Within this embodiment, the ready-to-use agent (a) is now prepared bymixing agents (a′) and (a″).

For example, the user can first mix or shake the agent (a′) comprisingthe organic silicon compound(s) (a1) with the aqueous effectpigment-comprising agent (a″). The user can now apply this mixture of(a′) and (a″) to the keratinous materials—either immediately after itspreparation or after a short reaction time of 10 seconds to 20 minutes.Afterwards, the user can apply agent (b) as described above.

The optionally included silicone polymer (a3) may be included in theagent (a′) or in the agent (a″). Preferably, the silicone polymer (a3)is included in the agent (a″).

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms and furthermore at least one silicone polymer        (a3), and    -   the second agent (a″) comprises at least one colorant compound        (a2) comprising at least one effect pigment which comprises α) a        substrate platelet and β) a coating, the coating having at least        one layer which is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        comprising,        (2) Application of the agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of 10 seconds to 10        minutes, preferably from 10 seconds to 5 minutes,        (4) if necessary, rinse the keratinous material with water,        (5) Application of agent (b) on the keratinous material,        (6) Allowing the agent (b) to act for a period of 30 seconds to        30 minutes, preferably from 30 seconds to 10 minutes,        (7) Rinse the keratinous material with water.

In the context of a further embodiment, particularly preferred is amethod comprising the following steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

-   -   the first agent (a′) comprises at least one organic silicon        compound (a1) from the group of silanes having one, two or three        silicon atoms, and    -   the second agent (a″) comprises at least one colorant compound        (a2) comprising at least one effect pigment which comprises a) a        substrate platelet and β) a coating, the coating having at least        one layer which is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and further comprises at least one silicone polymer (a3),        (2) Application of the agent (a) on the keratinous material,        (3) Allow the agent (a) to act for a period of 10 seconds to 10        minutes, preferably from 10 seconds to 5 minutes,        (4) if necessary, rinse the keratinous material with water,        (5) Application of agent (b) on the keratinous material,        (6) Allowing the agent (b) to act for a period of 30 seconds to        30 minutes, preferably from 30 seconds to 10 minutes,        (7) Rinse the keratinous material with water.

In a further preferred embodiment the silicone polymer(s) (a3) areprovided in a third separately prepared agent (a″′).

Preferred in the context of this further embodiment is a methodcomprising the following steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″) and a third agent (a″), whereinthe first agent (a′) comprises at least one organic silicon compound(a1) from the group of silanes having one, two or three silicon atoms,andthe second agent (a″) comprises at least one colorant compound (a2)comprising at least one effect pigment which comprises α) a substrateplatelet and β) a coating, the coating having at least one layer whichis(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigments comprising andthe third agent (a″) comprises at least one silicone polymer (a3),(2) Application of the agent (a) on the keratinous material,(3) Allow the agent (a) to act for a period of 10 seconds to 10 minutes,preferably from 10 seconds to 5 minutes,(4) if necessary, rinse the keratinous material with water,(5) Application of agent (b) on the keratinous material,(6) Allowing the agent (b) to act for a period of 30 seconds to 30minutes, preferably from 30 seconds to 10 minutes,(7) Rinse the keratinous material with water.

Multi-Component Packaging Unit (Kit-of-Parts)

To increase user comfort, the user is preferably provided with allrequired resources in the form of a multi-component packaging unit(kit-of-parts).

A second subject matter of the present disclosure is therefore amulti-component packaging unit (kit-of-parts) for coloring keratinicmaterial, comprehensively packaged separately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and    -   a third container comprising an agent (b), wherein the agent        comprises (b):        (b1) At least one sealing agent,        wherein the components (a1), (a2) and (b1) have been disclosed        in detail above.

The organic silicon compounds (a1) from the group of silanes with one,two or three silicon atoms included in the agent (a′) of the kitcorrespond to the organic silicon compounds (a1) that were also used inthe agent (a) of the previously described process.

The colorant compounds (a2) included in the agent (a″) of the kitcomprising at least one effect pigment which comprises α) a substrateplatelet and β) a coating, wherein the coating has at least one layerwhich is

(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigments corresponding to thecolorant compounds (a2) comprising an effect pigment which comprises α)a substrate platelet and β) a coating, wherein the coating has at leastone layer which is(i) a metal oxide and/or metal oxide hydrate and(ii) a coloring compound from the group of pigmentswhich were also used in agent (a) of the previously described process.

The sealing reagent (b1) included in agent (b) of the kit corresponds tothe sealing reagent that was also used in agent (b) of the previouslydescribed method.

In this context, it is again possible to use the optionally includedsilicone polymer (a3)

To be made up in the agent (a′), in the agent (a″) or in a further agent(a″).

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′): at least one organic silicon compound (a1) from        the group of silanes with one, two or three silicon atoms and        furthermore at least one silicone polymer (a3), and    -   a second container comprising an agent (a″), the agent        comprising (a″): (a2) at least one colorant compound comprising        at least one effect pigment comprising α) a substrate platelet        and β) a coating, wherein the coating has at least one layer        that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and    -   a third container comprising an agent (b), wherein the agent        comprises (b):        (b1) at least one sealing reagent,        wherein the components (a1), (a2), (a3) and (b1) have been        disclosed in detail above.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′): at least one organic silicon compound (a1) from        the group of silanes having one, two or three silicon atoms,    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and further comprises at least one silicone polymer (a3), and    -   a third container comprising an agent (a′″), wherein the agent        (a′″) is a water-comprising cosmetic carrier    -   a fourth container comprising agent (b), wherein the agent        comprises (b):        (b1) at least one sealing reagent,        wherein the components (a1), (a2), (a3) and (b1) have been        disclosed in detail above.

In this embodiment, agents (a′) and (a″) have a low water content. Toprepare the ready-to-use agent (a), agents (a′), (a″) and (a′″) aremixed. In this case, the agent (a″) represents a water-comprisingcosmetic carrier.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′): at least one organic silicon compound (a1) from        the group of silanes having one, two or three silicon atoms,    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments        and further comprises at least one silicone polymer (a3), and    -   a third container comprising an agent (b), wherein the agent        comprises (b):        (b1) at least one sealing reagent,        wherein the components (a1), (a2), (a3) and (b1) have been        disclosed in detail above.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′): at least one organic silicon compound (a1) from        the group of silanes having one, two or three silicon atoms,    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one colorant compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating has at least one layer that is        (i) a metal oxide and/or metal oxide hydrate and        (ii) a coloring compound from the group of pigments,    -   a third container comprising an agent (a′″), said agent        comprising (a′″): at least one silicone polymer (a3), and    -   a fourth container comprising agent (b), wherein the agent        comprises (b): (b1) at least one sealing reagent,        wherein the components (a1), (a2), (a3) and (b1) have been        disclosed in detail above.

In this embodiment of the multicomponent packaging unit, it may bepreferred that the agent (a′″) further comprises at least one furthercolorant compound (a2).

Concerning the further preferred embodiments of the multicomponentpackaging unit, mutatis mutantis what has been said about the processapplies.

EXAMPLES Example 1

The following formulations have been produced (unless otherwiseindicated, all figures are in % by weight)

Agent (a′) Agent (a′) wt..-% (3-Aminopropyl)triethoxysilane (a1) 20Methyltrimethoxysilane (a1) 70 Water ad 100

Agent (a″) Agent (a″) wt..-% Effect pigment according to claim 1 (a2) 5PEG-12 Dimethicone (a3) 5 Hydroxyethyl cellulose 1 Water ad 100

The ready-to-use agent (a) was prepared by mixing 5 g of agent (a′) and20 g of agent (a″). The pH value of the agent (a) was adjusted to avalue of 10.5 by adding ammonia or lactic acid. Then the agent (a) wasallowed to stand for about 5 minutes.

Agent (b) Agent (b) wt..-% Ethylene/Sodium Acrylate Copolymer (b1) 40(25% solution) Water ad 100

The agent (a) was massaged into one strand of hair at a time (Kerling,Euronatural hair white), and left to act for 1 minute. The agent (a) wasthen rinsed with water.

Subsequently, agent (b) was applied to the hair strand, left to act for1 minute and then also rinsed with water.

While at least one exemplary embodiment has been presented in theforegoing detailed description, it should be appreciated that a vastnumber of variations exist. It should also be appreciated that theexemplary embodiment or exemplary embodiments are only examples, and arenot intended to limit the scope, applicability, or configuration of thevarious embodiments in any way. Rather, the foregoing detaileddescription will provide those skilled in the art with a convenient roadmap for implementing an exemplary embodiment as contemplated herein. Itbeing understood that various changes may be made in the function andarrangement of elements described in an exemplary embodiment withoutdeparting from the scope of the various embodiments as set forth in theappended claims.

1. A process for dyeing keratinous material, comprising: applying an agent (a) to the keratinous material, wherein the agent (a) comprises: (a1) at least one organic silicon compound selected from the group of silanes having one, two or three silicon atoms, and (a2) at least one colorant compound comprising at least one effect pigment comprising α) a substrate platelet and β) a coating, wherein the coating has at least one layer that is (i) a metal oxide and/or metal oxide hydrate and (ii) a coloring compound chosen from the group of pigments; and applying an agent (b) to the keratinous material, wherein the agent (b) comprises: (b1) at least one sealing reagent.
 2. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of the formula (I) and/or (II) R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl group, L is a linear or branched divalent C₁-C₂₀ alkylene group, R₃, R₄ independently of one another represent a C₁-C₆ alkyl group, a stands for an integer from 1 to 3, and b stands for the integer 3−a, and wherein in the organic silicon compound of formula (II) (R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II), R₅, R₅′, R₅″, R₆, R₆′ and R₆″ independently represent a C₁-C₆ alkyl group, A, A′, A″, A′″ and A″″ independently represent a linear or branched divalent C₁-C₂₀ alkylene group, R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an amino C₁-C₆ alkyl group or a group of formula (III) -(A_(″″))-Si(R₆″)_(d)″(OR₅″)_(c)″  (III), c stands for an integer from 1 to 3, d stands for the integer 3−c, c′ stands ‘for an integer from 1 to 3, d′ stands for the integer 3−c′, c″ stands, for an integer from 1 to 3, d″ stands for the integer 3−c″, e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or 1, h stands for 0 or 1, provided that at least one of e, f, g and h is different from
 0. 3. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (I), R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ both represent a hydrogen atom, and L represents a linear, bivalent C₁-C₆-alkylene group, R₃, R₄ independently represent a methyl group or an ethyl group, a stands for the number 3 and b stands for the number
 0. 4. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (I) selected from the group of (3-Aminopropyl)triethoxysilane, (3-Aminopropyl)trimethoxysilane, 1-(3-Aminopropyl)silantriol, (2-Aminoethyl)triethoxysilane, (2-Aminoethyl)trimethoxysilane, 1-(2-Aminoethyl)silantriol, (3-Dimethylaminopropyl)triethoxysilane, (3-Dimethylaminopropyl)trimethoxysilane, 1-(3-Dimethylaminopropyl)silantriol, (2-Dimethylaminoethyl)triethoxysilane-, (2-dimethylaminoethyl)trimethoxysilane, and/or 1-(2-Dimethylaminoethyl)silantriol.
 5. The process according to claim 1, applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (II). (R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)—[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II), where e and f both stand for the number 1, g and h both stand for the number 0, A and A′ independently represent a linear, bivalent C₁-C₆ alkylene and R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).
 6. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (II) selected from the group of 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, 3-(Triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamine, N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propane-amine, 2-[Bis[3-(trimethoxysilyl) propyl]amino]-ethanol, 2-[Bis[3-(triethoxysilyl) propyl]amino]-ethanol, 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl) propyl]-1-propanamine, 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl) propyl]-1-propanamine, N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine, N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and/or N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.
 7. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (IV). R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV), where R₉ stands for a C₁-C₁₈ alkyl group, R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group, R₁₁ represents a C₁-C₆ alkyl group, k is an integer from 1 to 3, and m stands for the integer 3−k.
 8. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least one organic silicon compound (a1) of formula (IV) selected from the group of Methyltrimethoxysilane, Methyltriethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Propyltrimethoxysilane, Propyltriethoxysilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, Octyltrimethoxysilane, Octyltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, and Mixtures of these.
 9. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) comprising at least two structurally different organic silicon compounds (a1).
 10. The process of claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the substrate platelet comprises aluminum.
 11. The process of claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the metal oxide and/or metal oxide hydrate (i) is selected from the group of silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.
 12. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the metal oxide and/or metal oxide hydrate (i) is silicon dioxide.
 13. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the particle size D₉₀ of the colorant compound (ii) is smaller than the layer thickness of the at least one layer.
 14. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the agent (a) comprises at least one further coloring compound (a2).
 15. Kit-of-parts for dyeing keratinous material, comprising separately packaged a first container containing an agent (a′), wherein the agent comprises (a′): (a1) at least one organic silicon compound selected from the group of silanes having one, two or three silicon atoms, and a second container containing an agent (a″), the agent (a″) comprising: (a2) at least one colorant compound comprising at least one effect pigment comprising α) a substrate platelet and β) a coating, wherein the coating has at least one layer that is (i) a metal oxide and/or metal oxide hydrate and (ii) a coloring compound chosen from the group of pigments, a third container containing an agent (b), wherein the agent (b) comprises: (b1) at least one sealing reagent.
 16. The method according to claim 3, wherein the agent (a) comprises at least one organic silicon compound (a1) of formula (I), R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ both represent a hydrogen atom, and L represents a propylene group (—CH₂—CH₂—CH₂—) or an ethylene group (—CH₂—CH₂—),
 17. The process according to claim 1, wherein applying the agent (a) comprises applying the agent (a) wherein the particle size D₉₉ of the colorant compound (ii) is smaller than the layer thickness of the at least one layer.
 18. The process according to claim 14, wherein applying the agent (a) comprises applying the agent (a) wherein the at least one further coloring compound (a2) is selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and/or from colored mica- or mica-based pigments coated with at least one metal oxide and/or a metal oxychloride. 